Cyclopentadienyl/adamantyl phosphinimine zirconium and hafnium complexes

ABSTRACT

Provided in this disclosure are zirconium and hafnium complexes that contain 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one other ligand. The use of such a complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene, or 1-octene).

TECHNICAL FIELD

The present disclosure relates to new zirconium and hafnium complexeshaving a cyclopentadienyl ligand and an adamantyl phosphinimine ligandand olefin polymerization catalyst systems that employ these complexes.

BACKGROUND ART

Group 4 metal complexes having a cyclopentadienyl ligand and aphosphinimine ligand, and the use of such complexes as olefinpolymerization catalysts, is disclosed in U.S. Pat. No. 6,063,879(Stephan et al, to NOVA Chemicals International S.A.).

SUMMARY OF INVENTION

In one embodiment, the present disclosure provides a complex having theformula (Pl)(Cp)ML₂, wherein:

-   I) Pl is a phosphinimine ligand defined by the formula:

-   

-   where N is a nitrogen atom; P is a phosphorus atom; each R¹ is    unsubstituted adamantyl, or substituted adamantyl; and R^(1′) is    selected from the group consisting of unsubstituted adamantyl,    substituted adamantyl and C₁ to C₆ hydrocarbyl;

-   II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered    carbon ring having delocalized bonding within the ring and bound to    M, which ring is unsubstituted or may be further substituted;

-   III) each L is an activatable ligand; and

-   IV) M is zirconium or hafnium.

In another embodiment, the present disclosure provides an olefinpolymerization catalyst system comprising:

-   A) a complex having the formula (Pl)(Cp)ML₂, wherein:    -   I) Pl is a phosphinimine ligand defined by the formula:

    -   

    -   where N is a nitrogen atom; P is a phosphorus atom; each R¹ is        unsubstituted adamantyl, or substituted adamantyl; and R^(1′) is        selected from the group consisting of unsubstituted adamantyl,        substituted adamantyl and C₁ to C₆ hydrocarbyl;

    -   II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered        carbon ring having delocalized bonding within the ring and bound        to M, which ring is unsubstituted or may be further substituted;

    -   III) each L is an activatable ligand; and

    -   IV) M is zirconium or hafnium; and-   B) an activator.

In another embodiment, the present disclosure provides a process for thepolymerization of olefins comprising contacting one or more of ethyleneand C₃ to C₁₀ alpha olefins with an olefin polymerization catalystsystem under polymerization conditions; wherein the olefinpolymerization catalyst system comprises:

-   A) a complex having the formula (Pl)(Cp)ML₂, wherein:    -   I) PI is a phosphinimine ligand defined by the formula:

    -   

    -   where N is a nitrogen atom; P is a phosphorus atom; each R¹ is        unsubstituted adamantyl, or substituted adamantyl; and R^(1′) is        selected from the group consisting of unsubstituted adamantyl,        substituted adamantyl and C₁ to C₆ hydrocarbyl;

    -   II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered        carbon ring having delocalized bonding within the ring and bound        to M, which ring is unsubstituted or may be further substituted;

    -   III) each L is an activatable ligand; and

    -   IV) M is zirconium or hafnium; and-   B) an activator.

In an embodiment, the present disclosure provides a complex having theformula:

wherein each L is an activatable ligand; and wherein M is zirconium orhafnium.

In an embodiment, the present disclosure provides a complex having theformula:

wherein each L is an activatable ligand; and wherein M is zirconium orhafnium.

In another embodiment, the present disclosure provides an olefinpolymerization catalyst system comprising:

-   A) a complex having the formula:

-   

-   wherein each L is an activatable ligand; and wherein M is zirconium    or hafnium; and

-   B) an activator.

In another embodiment, the present disclosure provides an olefinpolymerization catalyst system comprising:

-   A) a complex having the formula:

-   

-   wherein each L is an activatable ligand; and wherein M is zirconium    or hafnium; and

-   B) an activator.

In another embodiment, the present disclosure provides a process for thepolymerization of olefins comprising contacting one or more of ethyleneand C₃ to C₁₀ alpha olefins with an olefin polymerization catalystsystem under polymerization conditions; wherein the olefinpolymerization catalyst system comprises:

-   A) a complex having the formula:

-   

-   wherein each L is an activatable ligand; and wherein M is zirconium    or hafnium; and

-   B) an activator.

In another embodiment, the present disclosure provides a process for thepolymerization of olefins comprising contacting one or more of ethyleneand C₃ to C₁₀ alpha olefins with an olefin polymerization catalystsystem under polymerization conditions; wherein the olefinpolymerization catalyst system comprises:

-   A) a complex having the formula:

-   

-   wherein each L is an activatable ligand; and wherein M is zirconium    or hafnium; and

-   B) an activator.

In an embodiment of the disclosure, an activator consists of acombination of an aluminoxane and an ionic activator (e.g., tritylborate, [Ph₃C][B(C₆F₅)₄]).

In an embodiment of the disclosure, an activator consists of acombination of an organoaluminum compound and an ionic activator (e.g.,trityl borate, [Ph₃C][B(C₆F₅)₄]).

DESCRIPTION OF EMBODIMENTS

As used herein the term “unsubstituted” means that hydrogen radicals arebonded to the molecular group that is referred to by the termunsubstituted. The term “substituted” means that the group referred toby this term possesses one or more moieties that have replaced one ormore hydrogen radicals in any position within the group; non-limitingexamples of moieties include halogen radicals (F, Cl, Br), an alkylgroup, an alkylaryl group, an arylalkyl group, an alkoxy group, an arylgroup, an aryloxy group, an amido group, a silyl group or a germanylgroup, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups,phosphine groups, phenyl groups, naphthyl groups, C₁ to C₁₀ alkylgroups, C₂ to C₁₀ alkenyl groups, and combinations thereof.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear or branched, aliphatic, olefinic,acetylenic and aryl (aromatic) radicals comprising hydrogen and carbonthat are deficient by one hydrogen. The term “cyclic hydrocarbyl group”connotes hydrocarbyl groups that comprise cyclic moieties and which mayhave one or more than one cyclic aromatic ring, and/or one or more thanone non-aromatic ring. The term “acyclic hydrocarbyl group” connoteshydrocarbyl groups that do not have cyclic moieties such as aromatic ornon-aromatic ring structures present within them.

As used herein, the term “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. The term “heteroatomcontaining” or “heteroatom containing hydrocarbyl group” means that oneor more than one non carbon atom(s) may be present in the hydrocarbylgroups. Some non-limiting examples of non-carbon atoms that may bepresent is a heteroatom containing hydrocarbyl group are N, O, S, P andSi as well as halides such as for example Br and metals such as Sn. Somenon-limiting examples of heteroatom containing hydrocarbyl groupsinclude for example imines, amine moieties, oxide moieties, phosphinemoieties, ethers, ketones, heterocyclics, oxazolines, thioethers, andthe like.

As used herein, an “alkyl radical” or “alkyl group” includes linear,branched and cyclic paraffin radicals that are deficient by one hydrogenradical; non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” or “alkenyl group” refers tolinear, branched and cyclic hydrocarbons containing at least onecarbon-carbon double bond that is deficient by one hydrogen radical. Theterm “alkynyl radical” or “alkynyl group” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon triple bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “alkylaryl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl. An “arylalkyl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

An “alkoxy” group is an oxy group having an alkyl group pendant therefrom; and includes for example a methoxy group, an ethoxy group, aniso-propoxy group, and the like.

An “aryloxy” group is an oxy group having an aryl group pendant therefrom; and includes for example a phenoxy group and the like.

Adamantyl Phosphinimine Ligand

The adamantyl phosphinimine ligand is defined as:

where N is a nitrogen atom; P is a phosphorus atom; each R¹ isunsubstituted adamantyl, or substituted adamantyl and R^(1′) is selectedfrom the group consisting of unsubstituted adamantyl, substitutedadamantyl and C₁ to C₆ hydrocarbyl.

For reference, the numbering of an adamantyl carbon atom frame, ineither an unsubstituted or a substituted adamantyl moiety, as referredto in the present disclosure is provided below:

In an embodiment of the disclosure, the term “unsubstituted adamantyl”as used in this disclosure has a narrow meaning - it is restricted tothe well-known hydrocarbon cage structure that contains 10 carbon atomsand excludes “substituted” adamantyl. Thus, the term unsubstitutedadamantyl as used herein excludes cage structures that contain more than10 carbon atoms and also excludes structures that contain atoms otherthan carbon and hydrogen atoms. It will be appreciated by those skilledin the art that there are two isomers of unsubstituted adamantyl, namely1-adamantyl (where the adamantyl moiety is bonded from a tertiary carbonatom to the phosphorus atom of the phosphinimine ligand) and 2-adamantyl(where the adamantyl moiety is bonded from a secondary carbon atom tothe phosphorus atom of the phosphinimine ligand).

In an embodiment, each of the unsubstituted adamantyl groups on thephosphinimine ligand is 1-adamantyl.

In an embodiment of the disclosure, the term “substituted adamantyl” asused in this disclosure means that the adamantyl has pendant from its 10carbon atom frame, one or more substituent(s). It will be appreciated bythose skilled in the art that there are two isomers of a substitutedadamantyl, namely substituted 1-adamantyl (where the substitutedadamantyl moiety is bonded from a tertiary carbon atom to the phosphorusatom of the phosphinimine ligand) and substituted 2-adamantyl (where thesubstituted adamantyl moiety is bonded from a secondary carbon atom tothe phosphorus atom of the phosphinimine ligand).

In an embodiment, each of the substituted adamantyl groups on thephosphinimine ligand is a substituted 1-adamantyl.

In an embodiment of the disclosure, a substituted adamantyl has one ormore hydrocarbyl group substituents.

In an embodiment of the disclosure, a substituted adamantyl has one ormore heteroatom containing hydrocarbyl group substituents.

In an embodiment of the disclosure, a substituted adamantyl has one ormore halide group substituents.

In an embodiment of the disclosure, a substituted adamantyl has one ormore alkyl group substituents.

In an embodiment of the disclosure, a substituted adamantyl has one ormore aryl group substituents.

In an embodiment of the disclosure, a substituted adamantyl has one ormore methyl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore hydrocarbyl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore heteroatom containing hydrocarbyl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore halide group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore alkyl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore aryl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has one ormore methyl group substituents.

In an embodiment of the disclosure, a substituted 1-adamantyl has amethyl group substituent at the 3-position and the 5-position.

In an embodiment of the disclosure, a substituted 1-adamantyl has amethyl group substituent at the 3-position, the 5-position, and the7-position.

In an embodiment, each R¹ is an unsubstituted adamantyl.

In an embodiment, each R¹ is a substituted adamantyl.

In an embodiment, each R¹ is an unsubstituted 1-adamantyl.

In an embodiment, each R¹ is a substituted 1-adamantyl.

In an embodiment, each R¹ is a substituted 1-adamantyl having methylgroup substituent at the 3-position and the 5-position.

In an embodiment, each R¹ is a substituted 1-adamantyl having a methylgroup substituent at the 3-position, the 5-position, and the 7-position.

In an embodiment, R^(1′) is an unsubstituted adamantyl.

In an embodiment, R^(1′) is a substituted adamantyl.

In an embodiment, R^(1′) is an unsubstituted 1-adamantyl.

In an embodiment, R^(1′) is a substituted 1-adamantyl.

In an embodiment, R^(1′) is a substituted 1-adamantyl having methylgroup substituent at the 3-position and the 5-position.

In an embodiment, R^(1′) is a substituted 1-adamantyl having a methylgroup substituent at the 3-position, the 5-position, and the 7-position.

In an embodiment, R^(1′) is a C₁ to C₆ hydrocarbyl.

Cyclopentadienyl-Type Ligand

The cyclopentadienyl-type ligands comprise a 5-membered carbon ringhaving delocalized bonding within the ring and bound to the metal, whichring is unsubstituted or may be further substituted (sometimes referredto in a short form as Cp ligands). Cyclopentadienyl-type ligands includeunsubstituted cyclopentadienyl, substituted cyclopentadienyl,unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl andsubstituted fluorenyl. Hydrogenated versions of indenyl and fluorenylligands are also contemplated for use in the current disclosure, so longas the five-carbon ring which bonds to the metal via eta-5 (or in somecases eta-3) bonding remains intact. An exemplary list of substituentsfor a cyclopentadienyl-type ligand includes the group consisting ofC₁₋₁₀ hydrocarbyl radicals (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₁₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a C₁₋₄ alkylradical; a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical; anamido radical which is unsubstituted or substituted by up to two C₁₋₈alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; silyl radicals of theformula -Si-(R)₃ wherein each R is independently selected from the groupconsisting of hydrogen, a C₁₋₈ alkyl or alkoxy radical, and C₆₋₁₀ arylor aryloxy radicals; siloxy radicals and germanyl radicals of theformula Ge-(R)₃ wherein R is as defined directly above. Thecyclopentadienyl-type ligands may also contain heterocyclic moieties orheteroatom containing hydrocarbyl groups.

In an embodiment of the disclosure, the cyclopentadienyl-type ligand ispentamethylcyclopentadienyl.

In an embodiment of the disclosure, the cyclopentadienyl-type ligand ispenta (n-propyl)cyclopentadienyl.

In an embodiment of the disclosure, the cyclopentadienyl-type ligand iscyclopentadienyl.

In an embodiment, the cyclopentadienyl-type ligand istetramethyl(pentafluorobenzyl)cyclopentadienyl, CpMe₄(CH₂C₆F₅).

In an embodiment, the cyclopentadienyl-type ligand is(pentafluorobenzyl)cyclopentadienyl, Cp(CH₂C₆F₅).

In an embodiment, the cyclopentadienyl-type ligand istetramethyl(3,5-tert-butylphenyl)cyclopentadienyl,CpMe₄(-3,5-t-B₂-C₆H₃).

In an embodiment of the disclosure, the cyclopentadienyl-type ligand is1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl.

Activatable Ligand

The term “activatable ligand” refers to a ligand which may be activatedby a cocatalyst (also referred to as an “activator”), to facilitateolefin polymerization. An activatable ligand L may be cleaved from themetal center M of the catalyst via a protonolysis reaction or abstractedfrom the metal center M by suitable acidic or electrophilic catalystactivator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand L may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g., a halide may be converted toan alkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins. In embodiments of the presentdisclosure, the activatable ligand, L is independently selected from thegroup consisting of a hydrogen atom; a halogen atom; a C₁₋₁₀ hydrocarbylradical; a C₁₋₁₀ alkoxy radical; a C₆₋₁₀ aryl oxide radical, each ofwhich said hydrocarbyl, alkoxy, and aryl oxide radicals may beunsubstituted by or further substituted by a halogen atom, a C₁₋₈ alkylradical, a C₁₋₈ alkoxy radical, a C₆₋₁₀ aryl or aryloxy radical; anamido radical which is unsubstituted or substituted by up to two C₁₋₈alkyl radicals; and a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals. Two activatable L ligandsmay also be joined to one another and form for example, a substituted orunsubstituted diene ligand (e.g., 1,3-diene); or a delocalizedheteroatom containing group such as an acetate group.

The number of activatable ligands depends upon the valency of the metaland the valency of the activatable ligand. In some embodiments, thepreferred phosphinimine catalysts are based on group 4 metals in theirhighest oxidation state (i.e., 4⁺). Particularly suitable activatableligands are monoanionic such as a halide (e.g., chloride) or ahydrocarbyl (e.g., methyl, benzyl).

In some instances, the metal of the phosphinimine catalyst may not be inthe highest oxidation state. For example, a hafnium(III) or a zirconium(III) component would contain only one activatable ligand.

In an embodiment of the disclosure, the activatable ligand, L is methyl.

In an embodiment of the disclosure, the activatable ligand, L is benzyl(“Bn” for short).

In an embodiment of the disclosure, the activatable ligand, L ischloride.

The Activator

In the present disclosure, the complex is used in combination with atleast one activator (or “cocatalyst”) to form an active polymerizationcatalyst system for olefin polymerization. Activators (i.e.,cocatalysts) include ionic activator cocatalysts and aluminoxanecocatalysts and may in some embodiments include organoaluminum compoundsas cocatalysts.

In an embodiment, the activator comprises one or more of the following:an aluminoxane compound, an ionic activator, an organoaluminum compound.A hindered phenol may optionally be used in combination with analuminoxane compound or an organoaluminum compound.

In an embodiment of the disclosure the activator is an organoaluminumcompound and an ionic activator. In an embodiment of the disclosure theactivator is an aluminoxane compound and an ionic activator. In anembodiment of the invention the activator is an ionic activator.

In an embodiment of the disclosure the activator is selected from thegroup consisting of an aluminoxane, an organoaluminum compound, an ionicactivator, and mixtures thereof.

Aluminoxane (Also Referred to as Alkylaluminoxane)

The activator used to activate the single site catalyst can be anysuitable activator including one or more activators selected from thegroup consisting of alkylaluminoxanes and ionic activators, optionallytogether with an alkylating agent. Without wishing to be bound bytheory, the alkylaluminoxanes are complex aluminum compounds of theformula: R⁴ ₂Al¹O(R⁴Al¹O)_(m)Al¹R⁴ ₂, wherein each R⁴ is independentlyselected from the group consisting of C₁₋₂₀ hydrocarbyl radicals and mis from 3 to 50. Optionally, a hindered phenol can be added to thealkylaluminoxane to provide a molar ratio of Al¹:hindered phenol of from2:1 to 5:1 when the hindered phenol is present.

In an embodiment of the disclosure, R³ of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

The alkylaluminoxanes are typically used in substantial molar excesscompared to the amount of group 4 transition metal in the single sitecatalyst. The Al¹:group 4 transition metal molar ratios may be from 5:1to 10,000:1, such as about 30:1 to 500:1.

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneactivator is often used in combination with activatable ligands such ashalogens.

Alternatively, the activator of the present disclosure may be acombination of an alkylating agent (which may also serve as a scavenger)with an activator capable of ionizing the group 4 metal of the singlesite catalyst (i.e., an ionic activator). In this context, the activatorcan be chosen from one or more alkylaluminoxane and/or an ionicactivator.

When present, the alkylating agent may be selected from the groupconsisting of (R*)_(p)MgX² _(2-p) wherein X² is a halide and each R* isindependently selected from the group consisting of C₁₋₁₀ alkyl radicalsand p is 1 or 2; R*Li wherein in R* is as defined previously,(R*)_(q)ZnX² _(2-q) wherein R* is as defined previously, X² is halogenand q is 1 or 2; (R⁴)_(s)Al²X² _(3-s) wherein R* is as definedpreviously, X² is halogen and s is an integer from 1 to 3. In someembodiments, R* is a C₁₋₄ alkyl radical, and X² is chlorine.Commercially available compounds include triethyl aluminum (TEAL),diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu)₂Mg), and butylethyl magnesium (BuEtMg or BuMgEt).

Organoaluminum Compound

In an embodiment, organoaluminum compounds are defined by the formula:

wherein R³ and R³ are each independently C₁ to C₂₀ hydrocarbyl groups; Xis a halide; m + n + p = 3; and m ≥ 1.

In an embodiment of the disclosure, the organoaluminum compound used isdefined by the formula:

wherein x is from 1 to 3, x+y=3, R⁴ is a C₁ to C₁₀ hydrocarbyl group,and R⁵ is an alkyl or an aryl group.

In particular embodiments, organoaluminum compounds includetriethylaluminum, triisobutyl aluminum, tri-n-octylaluminum and diethylaluminum ethoxide.

Ionic Activator

The ionic activator may be selected from the group consisting of: (i)compounds of the formula [R⁵]⁺ [B(R⁶)₄]⁻ wherein B is a boron atom, R⁵is a cyclic C₅₋₇ aromatic cation or a triphenyl methyl cation and eachR⁶ is independently selected from the group consisting of phenylradicals which are unsubstituted or substituted with from 3 to 5substituents selected from the group consisting of a fluorine atom, aC₁₋₄ alkyl or alkoxy radical which is unsubstituted or substituted by afluorine atom; and a silyl radical of the formula —Si—(R⁷)₃; whereineach R⁷ is independently selected from the group consisting of ahydrogen atom and a C₁₋₄ alkyl radical; and (ii) compounds of theformula [(R⁸)_(t)ZH]⁺ [B(R⁶)₄]⁻ wherein B is a boron atom, H is ahydrogen atom, Z is a nitrogen atom or phosphorus atom, t is 2 or 3 andR⁸ is selected from the group consisting of C₁₋₈ alkyl radicals, aphenyl radical which is unsubstituted or substituted by up to three C₁₋₄alkyl radicals, or one R⁸ taken together with a nitrogen atom may forman anilinium radical and R⁶ is as defined above; and (iii) compounds ofthe formula B(R⁶)₃ wherein R⁶ is as defined above.

In some embodiments, in the above compounds, preferably R⁶ is apentafluorophenyl radical, and R⁵ is a triphenylmethyl cation, Z is anitrogen atom and R⁸ is a C₁₋₄ alkyl radical or one R⁸ taken togetherwith a nitrogen atom forms an anilinium radical (e.g., PhR⁸ ₂NH⁺, whichis substituted by two R⁸ radicals such as for example two C₁₋₄ alkylradicals).

Examples of compounds capable of ionizing the single site catalystinclude the following compounds: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron,N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron, di-(isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammonium tetra (phenyl)boron,triphenylphosphonium tetra)phenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,tropillium tetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate, benzene (diazonium)tetrakispentafluorophenyl borate, tropilliumphenyltris-pentafluorophenyl borate, triphenylmethyliumphenyl-trispentafluorophenyl borate, benzene (diazonium)phenyltrispentafluorophenyl borate, tropillium tetrakis(2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl) borate, tropillium tetrakis(3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl) borate, tropillium tetrakis(1,2,2-trifluoroethenyl) borate, trophenylmethylium tetrakis(1,2,2-trifluoroethenyl) borate, benzene (diazonium) tetrakis(1,2,2-trifluoroethenyl) borate, tropillium tetrakis(2,3,4,5-tetrafluorophenyl) borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl) borate, and benzene (diazonium) tetrakis(2,3,4,5-tetrafluorophenyl) borate.

Commercially available activators which are capable of ionizing thegroup 4 metal of the single site catalyst include:

N,N-dimethylaniliniumtetrakispentafluorophenyl borate(“[Me₂NHPh][B(CeF₅)₄]”); triphenylmethylium tetrakispentafluorophenylborate (“[Ph₃C][B(C₆F₅)₄]”); and trispentafluorophenyl boron and MAO(methylaluminoxane) and MMAO (modified methylaluminoxane).

The ionic activators compounds may be used in amounts which provide amolar ratio of group 4 transition metal to boron that will be from 1:1to 1:6.

Optionally, mixtures of alkylaluminoxanes and ionic activators can beused as activators in the polymerization catalyst.

Hindered Phenol

Non-limiting example of hindered phenols which may be employed in someembodiments of the present invention include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

Catalyst System

The catalyst precursor, the activator, or the entire catalystcomposition may be impregnated onto a solid, inert support, in liquidform such as a solution, dispersion or neat liquid, spray dried, in theform of a prepolymer, or formed in-situ during polymerization.

In the case of a supported catalyst composition, the catalystcomposition may be impregnated in or deposited on the surface of aninert substrate such as silica, clay, carbon black, polyethylene,polycarbonate porous crosslinked polystyrene, porous crosslinkedpolypropylene, alumina, thoria, zirconia, or magnesium halide (e.g.,magnesium dichloride), such that the catalyst composition is between 0.1and 90 percent by weight of the total weight of the catalyst compositionand the support.

Polymerization Process

In general, the catalyst composition may be used for the polymerizationof olefins by any suspension, solution, slurry, or gas phase process,using known equipment and reaction conditions, and is not limited to anyspecific type of reaction system. Generally, olefin polymerizationtemperatures range from about 0° C. to about 200° C. at atmospheric,subatmospheric, or superatmospheric pressures. Slurry or solutionpolymerization processes may utilize subatmospheric or superatmosphericpressures and temperatures in the range of about 40° C. to about 110° C.A useful liquid phase polymerization reaction system is described inU.S. Pat. No. 3,324,095. Liquid phase reaction systems generallycomprise a reactor vessel to which olefin monomer and catalystcomposition are added, and which contains a liquid reaction medium fordissolving or suspending the polyolefin. The liquid reaction medium mayconsist of the bulk liquid monomer or an inert liquid hydrocarbon thatis nonreactive under the polymerization conditions employed. Althoughsuch an inert liquid hydrocarbon need not function as a solvent for thecatalyst composition or the polymer obtained by the process, it usuallyserves as solvent for the monomers employed in the polymerization. Amongthe inert liquid hydrocarbons suitable for this purpose are isopentane,hexane, cyclohexane, heptane, benzene, toluene, and the like. Reactivecontact between the olefin monomer and the catalyst composition shouldbe maintained by constant stirring or agitation. The reaction mediumcontaining the olefin polymer product and unreacted olefin monomer iswithdrawn from the reactor continuously. The olefin polymer product isseparated, and the unreacted olefin monomer and liquid reaction mediumare recycled into the reactor.

An embodiment of the disclosure is an olefin polymerization processcomprising contacting one or more of ethylene and C₃ to C₁₀ alphaolefins with the olefin polymerization catalyst system described hereinunder polymerization conditions.

An embodiment of the disclosure is an olefin polymerization processcomprising contacting one or more of ethylene and C₃ to C₁₀ alphaolefins with the olefin polymerization catalyst system described hereinunder solution phase polymerization conditions.

An embodiment of the disclosure is an olefin polymerization processcomprising contacting ethylene and one or more olefins selected from thegroup consisting of 1-butene; 1-hexene; and 1-octene with the olefinpolymerization catalyst system described herein under polymerizationconditions.

An embodiment of the disclosure is an olefin polymerization processcomprising contacting ethylene and one or more olefins selected from thegroup consisting of 1-butene; 1-hexene; and 1-octene with the olefinpolymerization catalyst system described herein under solution phasepolymerization conditions.

Gas Phase Polymerization

When gas phase polymerization is employed, pressures may be in the rangeof 1 to 1,000 psi, such as 50 to 400 psi, for example 100 to 300 psi,and temperatures in the range of 30° C. to 130° C., for example 65° C.to 110° C. Stirred or fluidized bed gas phase reaction systems areparticularly useful. Generally, a conventional gas phase, fluidized bedprocess is conducted by passing a stream containing one or more olefinmonomers continuously through a fluidized bed reactor under reactionconditions and in the presence of catalyst composition at a velocitysufficient to maintain a bed of solid particles in a suspendedcondition. A stream containing unreacted monomer is withdrawn from thereactor continuously, compressed, cooled, optionally fully or partiallycondensed as disclosed in U.S. Pat. Nos. 4,588,790 and 5,462,999, andrecycled to the reactor. Product is withdrawn from the reactor andmake-up monomer is added to the recycle stream. As desired fortemperature control of the system, any gas inert to the catalystcomposition and reactants may also be present in the gas stream.

Polymerization may be carried out in a single reactor or in two or morereactors in series and is conducted substantially in the absence ofcatalyst poisons. Organometallic compounds may be employed as scavengingagents for poisons to increase the catalyst activity. Examples ofscavenging agents are metal alkyls, including aluminum alkyls, such astriisobutylaluminum.

Conventional adjuvants may be included in the process, provided they donot interfere with the operation of the catalyst composition in formingthe desired polyolefin. Hydrogen or a metal or non-metal hydride (e.g.,a silyl hydride) may be used as a chain transfer agent in the process.Hydrogen may be used in amounts up to about 10 moles of hydrogen permole of total monomer feed.

Olefin polymers that may be produced according to the disclosureinclude, but are not limited to, ethylene homopolymers, homopolymers oflinear or branched higher alpha-olefins containing 3 to about 20 carbonatoms, and interpolymers of ethylene and such higher alpha-olefins, withdensities ranging from about 0.86 to about 0.96. Suitable higheralpha-olefins include, for example, propylene, 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene.Olefin polymers according to the disclosure may also be based on orcontain conjugated or non-conjugated dienes, such as linear, branched,or cyclic hydrocarbon dienes having from about 4 to about 20 carbonatoms, for example 4 to 12 carbon atoms. In some embodiments, preferreddienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene,1,7-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene,isobutylene, isoprene, ethylidene norbornene and the like. Aromaticcompounds having vinyl unsaturation such as styrene and substitutedstyrenes, and polar vinyl monomers such as acrylonitrile, maleic acidesters, vinyl acetate, acrylate esters, methacrylate esters, vinyltrialkyl silanes and the like may be polymerized according to thedisclosure as well. Specific olefin polymers that may be made accordingto the disclosure include, for example, polyethylene, polypropylene,ethylene/propylene rubbers (EPR’s), ethylene/propylene/diene terpolymers(EPDM’s), polybutadiene, polyisoprene and the like.

Slurry Phase Polymerization

Detailed descriptions of slurry polymerization processes are widelyreported in the patent literature. For example, particle formpolymerization, or a slurry process where the temperature is kept belowthe temperature at which the polymer goes into solution is described inU.S. Pat. No. 3,248,179. Slurry processes include those employing a loopreactor and those utilizing a single stirred reactor or a plurality ofstirred reactors in series, parallel, or combinations thereof.Non-limiting examples of slurry processes include continuous loop orstirred tank processes. Further examples of slurry processes aredescribed in U.S. Pat. No. 4,613,484.

Slurry processes are conducted in the presence of a hydrocarbon diluentsuch as an alkane (including isoalkanes), an aromatic, or a cycloalkane.The diluent may also be the alpha olefin comonomer used incopolymerizations. Alkane diluents include propane, butanes, (i.e.,normal butane and/or isobutane), pentanes, hexanes, heptanes andoctanes. The monomers may be soluble in (or miscible with) the diluent,but the polymer is not (under polymerization conditions). Thepolymerization temperature can be from about 5° C. to about 200° C. Insome embodiments, the polymerization temperature is less than about 120°C., such as from about 10° C. to about 100° C. The reaction temperatureis selected so that an ethylene copolymer is produced in the form ofsolid particles. The reaction pressure is influenced by the choice ofdiluent and reaction temperature. For example, pressures may range from15 to 45 atmospheres (about 220 to 660 psi or about 1,500 to about 4,600kPa) when isobutane is used as diluent to approximately twice that(i.e., from 30 to 90 atmospheres - about 440 to 1,300 psi or about 3,000to 9,100 kPa) when propane is used (see, for example, U.S. Pat. No.5,684,097). The pressure in a slurry process must be kept sufficientlyhigh to keep at least part of the ethylene monomer in the liquid phase.The reaction typically takes place in a jacketed closed loop reactorhaving an internal stirrer (e.g., an impeller) and at least one settlingleg. Catalyst, monomers and diluents are fed to the reactor as liquidsor suspensions. The slurry circulates through the reactor and the jacketis used to control the temperature of the reactor. Through a series oflet down valves the slurry enters a settling leg and then is let down inpressure to flash the diluent and unreacted monomers and recover thepolymer generally in a cyclone. The diluent and unreacted monomers arerecovered and recycled back to the reactor.

Solution Phase Polymerization

Solution processes for the copolymerization of ethylene and an alphaolefin having from 3 to 12 carbon atoms are well known in the art. Theseprocesses are conducted in the presence of an inert hydrocarbon solventtypically a C₅₋₁₂ hydrocarbon which may be unsubstituted or substitutedby a C₁₋₄ alkyl group, such as pentane, methyl pentane, hexane, heptane,octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. Anexample of a suitable solvent which is commercially available is ISOPAR®E (C₈-₁₂ aliphatic solvent, Exxon Chemical Co.).

In general, a solution polymerization process may use one, two (or more)polymerization reactors.

In an embodiment, the polymerization temperature in at least one CSTR(continuous stirred tank reactor) is from about 80° C. to about 280° C.(e.g., from about 120° C. to 220° C.) and a tubular reactor is operatedat a slightly higher temperature. Cold feed (i.e., chilled solventand/or monomer) may be added to the CSTR(s). The polymerization enthalpyheats the reactor. The polymerization solution which exits in thereactor may be more than 100° C. hotter than the reactor feedtemperature. Agitation efficiency in the CSTR may be determined bymeasuring the reactor temperature at several different points. Thelargest temperature difference (i.e., between the hottest and coldesttemperature measurements) is described as the internal temperaturegradient for the polymerization reactor. A very well mixed CSTR has amaximum internal temperature gradient of less than 10° C. An exampleagitator system is described in commonly assigned U.S. Pat. No.6,024,483. In some embodiments, preferred pressures are from about 500psi to 8,000 psi. In some embodiments, the preferred reaction process isa “medium pressure process”, which means that the pressure in eachreactor is less than about 6,000 psi (about 41,000 kilo Pascals orkPa)—for example, from about 1,500 psi to 3,000 psi (about 10,000 -21,000 kPa).

If more than one CSTR is employed, catalyst can be added to each of theCSTR(s) in order to maintain a high reactor rate. The catalyst used ineach CSTR may be the same or different, but it is generally preferableto use the same type of catalyst in each CSTR. In some embodiments, atleast 60 weight% of the ethylene fed to the CSTR(s) is polymerized topolyethylene in the CSTR(s). For example, at least 70 weight% of theethylene fed to the CSTR(s) can be polymerized to polyethylene in theCSTR(s).

If it is desired to use a mixed catalyst system in which one catalyst isa single site catalyst (for example, where the catalyst is a complexaccording to this disclosure) and one catalyst is a Ziegler-Natta (Z/N)catalyst, then the single site catalyst can be employed in the firstCSTR and the Z/N catalyst can be employed in the second CSTR.

A tubular reactor that is connected to the discharge of the at least onCSTR may also be employed. If two CSTR’s are used in series, then thetubular reactor receives the discharge from the second CSTR.

The term “tubular reactor” is meant to convey its conventional meaning:namely a simple tube. The tubular reactor of this disclosure will have alength/diameter (L/D) ratio of at least 10/1. The tubular reactor is notagitated. The tubular reactor can be operated adiabatically. Thus, aspolymerization progresses, the remaining comonomer is increasinglyconsumed and the temperature of the solution increases (both of whichimprove the efficiency of separating the remaining comonomer from thepolymer solution). The temperature increase along the length of thetubular reactor may be greater than 3° C. (i.e., that the dischargetemperature from the tubular reactor is at least 3° C. greater than thedischarge temperature from the CSTR that feeds the tubular reactor).

Optionally, the tubular reactor may also have feed ports for additionalcatalyst, cocatalyst, comonomer and/or telomerization agent (such ashydrogen). However, in some embodiments, preferably no additionalcatalyst is added to the tubular reactor.

The total volume of the tubular reactor can be at least 10 volume% ofthe volume of the at least one CSTR, especially from 30% to 200% (forclarity, if the volume of the CSTR is 1,000 liters, then the volume ofthe tubular reactor is at least 100 liters; for example, from 300 to2,000 liters).

Addition of Monomers and Solvent

Suitable monomers for copolymerization with ethylene include C₃₋₁₂ alphaolefins which are unsubstituted or substituted by up to two C₁₋₆ alkylradicals. Illustrative non-limiting examples of such alpha-olefins areone or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and1-decene. In some embodiments, octene-1 is preferred.

In an embodiment, the monomers are dissolved/dispersed in the solventeither prior to being fed to the first CSTR (or for gaseous monomers themonomer may be fed to the reactor so that it will dissolve in thereaction mixture). Prior to mixing, the solvent and monomers aregenerally purified to remove potential catalyst poisons such as water,oxygen or other polar impurities. The feedstock purification followsstandard practices in the art, e.g., molecular sieves, alumina beds andoxygen removal catalysts are used for the purification of monomers. Thesolvent itself as well (e.g., methyl pentane, cyclohexane, hexane ortoluene) can be treated in a similar manner.

Generally, the catalyst components may be premixed in the solvent forthe reaction or fed as separate streams to each reactor.

In some instances, premixing may be desirable to provide a reaction timefor the catalyst components prior to entering the first CSTR. Such an“in-line mixing” technique is described in the patent literature (mostnotably U.S. Pat. No. 5,589,555, issued Dec. 31, 1996 to DuPont CanadaInc.).

The residence time in each reactor will depend on the design and thecapacity of the reactor. Generally, the reactors can be operated underconditions to achieve a thorough mixing of the reactants. As previouslynoted, the polymerization reactors are arranged in series (i.e., withthe solution from the at least one CSTR being transferred to the tubularreactor).

EXAMPLES General Experimental Methods

All reactions were performed under purified nitrogen using standardSchlenk techniques or in an inert atmosphere glovebox. All solvents werepurified by the system described (Pangborn, A. B.; Giardello, M. A.;Grubbs, R. H.; Rosen R. K.; Timmers, F. J. Organometallics 1996, 15,1518-1520; D. Bradley G. Williams and Michelle Lawton, J. OrganicChemistry, 2010, 75, 8351-8354) and then stored over activated molecularsieves in either a Kontes flask or in an inert atmosphere glovebox(i.e., pentane, heptane, toluene, tetrahydrofuran, dichloromethane).Chloroform was used as received from Sigma Aldrich. Anhydrous methanoland ethanol were distilled from sodium. Phosphorous chloride,adamantane, aluminium chloride, lithium aluminium hydride, silvertrifluorormethane sulfonate, 1-adamantol, trimethylsilyltrifluoromethane sulfonate, and cyclopentadienyltitanium trichloridewere used as received from Sigma Aldrich. Triethylamine was purchasedfrom Sigma Aldrich and distilled over activated molecular sieves priorto use. Deuterated solvents (tetrahydrofuran-d₈, toluene-d₈) werepurchased from Aldrich and stored over activated 4 Å molecular sieves.Deuterated solvent (acetone-d₆, bromobenzene-d₅, chloroform-d,dichloromethane-d₂, tetrahydrofuran-d₈, toluene-d_(B)) were purchasedfrom Cambridge Isotope and stored over activated 4 Å molecular sieves.NMR spectra were recorded on a Bruker 400 MHz spectrometer (¹H: 400.1MHz, ¹⁹F: 376 MHz, ³¹P: 162 MHz). Cp*(tBu₃PN)Hf(CH₂Ph)₂ was preparedfrom Cp*(tBu₃PN)HfCl₂ (Can. J. Chem. 2009, 87, 1163-1172) and benzylmagnesium chloride.

Molecular weight information (M_(w), M_(n) and M_(z) in g/mol) andmolecular weight distribution (M_(w)/M_(n)), and z-average molecularweight distribution (Mz/Mw) were analyzed by gel permeationchromatography (GPC), using an instrument sold under the trade name“Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in this solventand were run without filtration. Molecular weights are expressed aspolyethylene equivalents with a relative standard deviation of 2.9% forthe number average molecular weight (“Mn”) and 5.0% for the weightaverage molecular weight (“Mw”). Polymer sample solutions (1 to 2 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourSHODEX® columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with CIRRUS® GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

Comonomer Content by Fourier Transform Infrared (FTIR) Spectroscopy: Thequantity (mol % (or wt %)) of comonomer in an ethylene interpolymerproduct was determined by FTIR and reported as the Short Chain Branching(SCB) content having dimensions of CH₃#/1000C (number of methyl branches(or short chain branches, SCB) per 1000 carbon atoms). This test wascompleted according to ASTM D6645-01 (2001), employing a compressionmolded polymer plaque and a Thermo-Nicolet 750 Magna-IRSpectrophotometer. The polymer plaque was prepared using a compressionmolding device (Wabash-Genesis Series press) according to ASTM D4703-16(April 2016).

Preparation of Bis(1-adamantyl)phosphinic Chloride

At ambient temperature, phosphorous chloride (100 g; 728 mmol) was addedto adamantane (27 g; 198 mmol; 1.06 equiv.) and aluminum chloride (25 g,187 mmol) with a large stir bar for effective stirring. The solution wasstirred overnight at 90° C. The reaction was cooled off and the excessphosphorous chloride was removed via distillation. Degassed chloroform(60 mL) was added to form a slurry. The slurry was cooled to 0° C. anddegassed water (300 mL) was added dropwise with vigorous stirring for 30minutes. The slurry was filtered and filtrated was separated. Theorganic layer was collected. The aqueous layer was extracted withdichloromethane. The chloroform and dichloromethane solutions werecombined and dried over MgSO₄. A white solid (27.0 g, 41%) was obtainedafter volatiles were pumped off.

Preparation of Bis(1-adamantyl)phosphine

To a solution of the bis(1-adamantyl)phosphinic chloride (27.0 g, 76mmol) in THF (200 mL) at -40° C. was added lithium aluminium hydride(7.25 g, 191 mmol) as a solid in small portions over 1.5 hours in aglove box. The slurry was allowed to warm to ambient temperatureovernight. The solution was filtered to remove the grey solid. Thefiltrate was pumped to dryness. The product was extract four times withpentane (4×200 mL) and pentane was evaporated to give a white solid(19.7 g, 86 %). ¹H NMR (CD₂Cl₂, δ, ppm): 2.78 (d, J_(PH) = 208 Hz, H),1.91 (m, 18H), 1.72 (s, 12H). ³¹P{¹H} NMR (CD₂Cl₂, δ, ppm)_(:) 17.70(s).

Preparation of 1-adamantylacetate

At ambient temperature, silver trifluorormethane sulfonate (0.040 g,0.16 mmol; 0.01 equivalent) was added to a mixture of 1-adamantanol(2.35 g; 15.4 mmol; 1.00 equiv.) and acetic anhydride (2.2 mL, 23.3mmol; 1.50 equiv.). The reaction was stirred at 60° C. overnight. Thereaction was cooled to ambient temperature and a solution of saturatedaqueous sodium bicarbonate (2.5 mL) was added. The reaction was stirredfor 30 minutes and extracted with pentane (3×10 mL). The organic layerswere combined and dried over MgSO₄. The organic layer was filtered andvolatiles were removed to give a colourless, clear liquid (0.91 g, 91%).¹H NMR (CD₂Cl₂, δ, ppm): 2.14 (br, 3H), 2.09 (s, 6H), 1.92 (s, 3H), 1.66(s, 6H).

Preparation of Tri(1-adamantyl)phosphine

At ambient temperature, trimethylsilyl trifluoromethane sulfonate (8.5mL; 46.5 mmol; 1.20 equiv.) was added to a solution ofbis(1-adamantyl)phosphine (11.75 g; 38.9 mmol; 1.00 equiv.) and1-adamantylacetate (8.30 g; 46.5 mmol; 1.10 equiv.) in dichloromethane(100 mL). The reaction was allowed to stir at ambient temperature over24 hours. Trimethylamine (26 mL; 187 mmol; 4.83 equiv.) was addeddropwise and the reaction was stirred for 30 minutes. The volatiles wereremoved in vacuo. The residue was slurried in toluene and filtered off awhite solid. The solid was slurried in degassed ethanol and filtered.The white solid was washed with ethanol (3×50 mL) and dried under vacuumto give pure tri(1-adamantyl)phosphine (15.79 g, 93%). ¹H NMR (CD₂Cl₂,δ, ppm): 2.21 (br, 18H), 1.92 (s, 9H), 1.74 (quartet, 18H). ³¹P{¹H} NMR(CD₂Cl₂, δ, ppm): 59.23.

Preparation of N-trimethylsilyl Tri(1-adamantyl)phosphinimine

To a solution of tri(1-adamantyl)phosphine (10.0 g; 23.0 mmol) intoluene (250 mL) at ambient temperature was add trimethylsilylazide (3mL). The reaction was heated to 90° C. and then 9 mL oftrimethylsilylazide was added for a total of 12 mL oftrimethylsilylazide (12 mL, 90.4 mmol, 3.95 equiv.). The reaction washeated to reflux at 110° C. for 4 hours. The reaction was cooled toambient temperature and the volatiles were removed in vacuo to give awhite solid (11.45 g, 95 %). ¹H NMR (toluene-d₈, δ, ppm): 2.31 (br,18H), 1.92 (s, 9H), 1.74 (quartet, 18H), 0.47 (s, 9H). ³¹P{¹H} NMR(toluene-d₈, δ, ppm): 19.3 (s).

Preparation of Tri(1-adamantyl)phosphinimine

To a solution of Trimethylsilyl tri(1-adamantyl) phosphinimine (7.09 g,13.5 mmol; 1.00 equiv.) and cesium fluoride (4.26 g, 28.0 mmol; 2.07equiv.) in THF (200 mL) was added methanol (200 mL) at ambienttemperature. The reaction was heated to 60° C. overnight. The reactionwas cooled to ambient temperature and the volatiles were removed invacuo. The white residue was slurried in dichloromethane (25 mL) andfiltered via cannula filtration. The solid was washed four times withdichloromethane (4×10 mL). The filtrate was pumped to dryness to offer awhite solid (0.99 g, 100%). ¹H NMR (CD₂Cl₂, δ, ppm): 2.30 (br, 18H),1.99 (s, 9H), 1.74 (quartet, 18H), -0.26 (s, 1H). ³¹P{¹H} NMR (CD₂Cl₂,δ, ppm): 45.59.

Preparation of Lithium Tri(1-adamantyl)phopshinimine Salt

To a slurry of tri(1-adamantyl) phosphinimine (1.63 g; 3.61 mmol) inpentane (60 mL) was added n-butyllithium (1.6 M in hexanes, 2.60 mL,1.15 equiv.) dropwise over 10 mins at ambient temperature in a glovebox. The slurry stirred overnight and cooled in a -35° C. freezer for 5hours and was filtered. The solid was washed with cold pentane (-35° C.,2x30 mL) and was dried under vacuum (1.53 g). ¹H NMR (THF-d₈, δ, ppm):2.34 (br.s,18H), 1.93 (d, 9H), 1.76 (d,9H) 1.70 (s, 6H). ³¹P{¹H} NMR(THF-d₈, δ, ppm): 42.15 (s).

Preparation ofPentamethylcyclopentadienyltri(1-adamantyl)phosphiniminate HafniumDichloride, Cp*(Ad₃PN)HfCl₂ (Ad = 1-Adamantyl; Cp* =Pentamethylcyclopentadienyl)

nBuLi (1.6, 1.38 mL, 2.21 mmol) was added to a slurry oftri(1-adamantyl)phosphinimine (0.994 g, 2.20 mmol) in toluene (40 mL) ina glove box. The reaction was stirred at room temperature for 1 hour toproduce a slurry of Ad₃P═NLi (Ad— 1-adamantyl) in toluene. This slurryof Ad₃P═NLi was added slowly to a stirred solution of Cp*HfCl₃ intoluene (~30 mL) at -70° C. The reaction was warmed to room temperatureand was stirred overnight. LiCl produced was filtered off and thefiltrate was concentrated by vacuum pumping to about 10 mL. Productcrystallized in about 8 hours. Pentane (10 mL) was added dropwise to thesupernatant causing more product to crystallize. The mother liquor wasdecanted and the solid was washed with pentane/toluene mixture (50/50,50 mL) and dried under vacuum (1.25 g). ¹H NMR (toluene-ds, δ, ppm):2.70-2.30 (very broad s.,18H), 2.26 (s, 15H), 1.95 (broad s, 9H),1.84-1.67 (very broad s, 6H), 1.615 (broad doublet, 9H, J = 9 Hz).³¹P{¹H} NMR (toluene-d₈, δ, ppm): 29.8 (s).

Preparation of Dimethyl PentamethylcyclopentadienylTri(1-adamantyl)Phosphiniminate Hafnium

To a solution of Cp*(1—Ad₃PN)HfCl₂ (644 mg; 0.77 mmol) in toluene (20mL) was added methylmagnesium bromide (0.90 mL; 2.70 mmol; 3.50 equiv.;3.0 M in diethyl ether) at ambient temperature. The mixture was stirredfor 2 hours followed by vacuum solvent removal. The residue wastriturated in toluene (20 mL) and reduced to dry under vacuum. Toluene(50 mL) was added, and the slurry mixture was filtered. White, finesolid (594 mg, 97%) was collected via recrystallization from thefiltrate. ¹H NMR (toluene-d₈, δ, ppm): 2.43 (s, broad, 18H), 2.16 (s,15H), 1.96 (s, broad, 9H), 1.69 (dd, J = 50.2 Hz, 18H), -0.03 (s, 6H).³¹P{¹H} NMR (toluene-d₈, δ, ppm): 25.06 (s).

Preparation of Dibenzyl PentamethylcyclopentadienylTri(1-adamantyl)Phosphiniminate Hafnium

Benzylmagnesium chloride in diethyl ether (1.0 M, 5 mL, 5 mmol) wasadded to a toluene solution of Cp*(1—Ad₃PN)HfCl₂ (1.4 g, 1.68 mmol) intoluene (30 mL) at room temperature. The mixture was stirred overnightand was pumped to dryness. Toluene (30 mL) was added to the residue tomake a slurry which was filtered to remove solid. The solid was rinsedwith toluene (10 mL). The filtrate was pumped to dryness and toluene (30mL) was added to make a solution, which was pumped to dryness again.Toluene (30 mL) was added again to the solid to make a solution, whichwas filtered to remove very small amount of solid. The filtrate wasconcentrated to about 5 mL and heptane was added. Product crystallizedas a white solid at -35° C. (0.74 g). ¹H NMR (toluene-ds, δ, ppm): 2.43(s, broad, 18H), 2.16 (s, 15H), 1.96 (s, broad, 9H), 1.69 (dd, J= 50.2Hz, 18H), -0.03 (s, 6H). ³¹P{¹H} NMR (toluene-d₈, δ, ppm): 25.06 (s).

Preparation of Bis(3,5-dimethyl-1-adamantyl) Phosphine,(3,5-Me₂-1-Ad)₂PH)

1,3-dimethyladamantane (10 g, 60.86 mmol) and AlCl₃ (9.5 g, 71 mmol)were weighed into a 150 mL Schlenk flask with a large stir bar. PCl₃ (40mL) was added to the flask. The mixture was stirred and was heated to90° C. overnight. An orange slurry produced. The excess PCl₃ wasdistilled out at 115-120° C. The flask was cooled to room temperatureand degassed chloroform (100 mL) was added. The flask was cooled to 0°C., and degassed water (20 mL) was added under nitrogen dropwise from asyringe over about 1 hour. An additional 15 mL of water was added to thequenched reaction. The content was filtered through a medium glass fritin air and the solid was rinsed with dichloromethane (~50 mL). Theorange filtrate was collected, dried with anhydrous magnesium chloride,and was filtered. The dried filtrate was pumped to dryness to givecrystalline (3,5-Me₂-1-Ad)₂P(O)Cl (15.77 g) which was used as is in thenext reaction.

The product from the last reaction was dissolved in THF (150 mL). Thesolution was cooled to -10° C. in a glove box. LiAlH₄ (3.5 g, excess) inTHF (~50 mL) was added from a dropping funnel in about 1 hour. Thereaction was stirred overnight. The next morning, the temperature wasraised to 40° C. for 2 hours. The solvent was pumped off. The residuewas extracted with pentane (3×100 mL) and the pentane solution waspumped to dryness to give the product, 3,5-Me₂-1-Ad)₂PH, as acrystalline solid (8.0 g). ¹H NMR (toluene-ds, d, ppm): 2.92 (d, J =201.64 Hz, 1H), 1.97-1.89 (m, 2H), 1.87-1.68 (m, 4H), 1.65-1.55 (m, 4H),1.55-1.44 (m, 4H), 1.32-1.15 (m, 8H), 1.01 (s, 4H), 0.78(s, 12H). ³¹PNMR (toluene-ds, d, ppm): 14.70 (s).

Preparation of (1-adamantyl)bis(3,5-dimethyl-1-adamantyl)Phosphine,(1-Ad) (3,5-Me₂-1-Ad)₂P

Bis(3,5-dimethyl-1-adamantyl) Phosphine (13.95 mmol) and1-adamantylacetate (2.87 g, 14.78 mmol) were weighed into a 250 mL roundbottomed flask, in which 50 mL of dichloromethane was added.Trimethylsilyl trifluoromethanesulfonate (3.38 g, 15.20 mmol) was added.The solution was stirred for 24 hours and triethylamine (7.05 g, 70mmol) was added to the solution. The solution was stirred for 0.5 hoursand was pumped to dryness. The solid was extracted with degassed ethanolat 65° C. (3×100 mL) and was filtered. The solid (which was not solublein EtOH) was dried under vacuum (3.50 g, 51 % yield). ¹H NMR(toluene-ds, d, ppm): 2.37 (br.s, 8H), 2.17 (br.s, 6H), 1.97 (dd, J = 33Hz, J = 15 Hz, 15H), 1.73 (dd, J = 45, J = 12 Hz, 7H), 1.32 (dd, J = 35Hz, J = 12 Hz, 7H), 1.075 (dd, J = 30, J = 10, 10H), 0.847 (s, 12H). ³¹PNMR (toluene-d₈, d, ppm): 55.9 (s).

Preparation of(1-adamantyl)bis(3,5-dimethyl-1-adamantyl)(N-trimethylsilyl)phosphinimine,(1-Ad) (3,5-Me₂-1-Ad)₂)P=NSiMe₃

Adamantyl)bis(3,5-Me₂-1-adamantyl)₂phosphine (3.50 g, 7.10 mmol) wasweighed into a 250 mL Schlenk flask. Toluene (~70 mL) and trimethylsilylazide (3.0 mL, 21.3 mmol) were added. The mixture was heated at 110° C.for 6 hours and the contents were pumped to dryness to give a foam whichsolidified to give a white solid (quantitative yield). ¹H NMR(toluene-ds, d, ppm): 2.361 (br.s, 8H), 2.159 (br.s, 5H), 2.08-1.89 (m,14H), 1.69 (dd, J = 44 Hz, J = 12 Hz, 8H), 1.29 (dd, J = 51 Hz, J = 12Hz, 11H), 1.065 (dd, J = 33 Hz, J = 13 Hz, 6H), 0.854 (s, 12H), 0.450(s, 9H). ³¹P NMR (toluene-ds, d, ppm): 18.7 (s).

Preparation of (1-adamantyl)bis(3,5-dimethyl-1-adamantyl)phosphinimine,(1-Ad) (3,5-Me₂-1-Ad)₂)P=NH

Adamantyl)bis(3,5-dimethyl-1-adamantyl)(N-trimethylsilyl)phosphinimineAd′₂)(1—Ad)P═NSiMe₃ (0.985 g, 1.70 mmol) was weighed into a 100 mLSchlenk flask. THF (40 mL) was added. Dry CsF (0.90 g, 5.9 mmol) wasweighed into a 50 mL hypo vial to which 35 mL degassed absolute MeOH wasadded to dissolve the CsF. The methanol solution was transferred to theSchenk flask and the mixture was stirred at 60° C. under 3 psi ofnitrogen for 6 hours. The solution was pumped to dryness and the residuewas extracted with 80 mL of pentane. The pentane solution was filtered,and the filtrate was pumped to dryness to give 0.80 g pure product. ¹HNMR (toluene-d₈, d, ppm): 2.41 (br.s, 6H), 2.21 (br.s, 4H), 2.08-1.96(m, 10H), 1.91 (br.s, 3H), 1.68 (dd, J = 42 Hz, J = 13 Hz, 6H), 1.273(dd, J = 57 Hz, J = 13 Hz, 9H), 1.04 (dd, J = 30 Hz, J = 13 Hz, 4H),0.836 (s, 12H), -0.45 (v.br.s, 1H). ³¹P NMR (toluene-ds, d, ppm): 41.6(s).

Preparation of(pentamethylcyclopentadienyl)(1-adamantyl)bis(3,5-dimethyl-1-adamantyl)phosphiniminatezirconium dichloride, Cp*[(1-Ad)(3,5-Me2-1-Ad)₂PN]ZrCl₂

[Ad′₂)(1—Ad)P═NH (1.085 g, 2.13 mmol) (1-Ad′ is3,5-dimethyl-1-adamantyl) was weighed in a 100 mL hypo vial and toluene(40 mL) was added. nBuLi in hexanes (1.6 M, 1.45 mL) was added dropwiseto the stirred slurry. In about 10 minutes, the slurry became a clearsolution which was stirred overnight.

Pentamethylcyclopentadienylzirconium trichloride (0.709 g, 2.13 mmol)was weighed into a 100 mL Schlenk flask and toluene (25 mL) was added.The solution was stirred for about 10 minutes and was cooled to -78° C.for 0.5 hours. The solution in the hypo vial containing[(1-Ad′₂)(1—Ad)P═NLi was transferred dropwise to the Schlenk flaskthrough a 20-gauge cannula over 10 minutes. The vial was rinsed withtoluene (2×4 mL) and the toluene washings was added to the Schlenkflask. After the reaction was stirred at -78° C. for about 10 minutes,the cold bath was removed, and the reaction was stirred at roomtemperature for 24 hours. No precipitate was observed. At about 28hours, the solution started to turn cloudy. The reaction was stirred foran additional 3 hours and the solution was filtered through celite toremove LiCl. The filtrate was pumped to remove toluene and a thick oilwas obtained. Pentane (about 5 mL) was added until the solution becamecloudy. The solution was put in a -35° C. freezer overnight and theproduct solidified. The mother liquor was pipetted out and the solid waswashed with pentane to give 1.39 g white solid. ¹H NMR (toluene-ds, d,ppm): 2.8-2.3 (br.s, 8H), 2.24 (s, 15H), 2.20 (s, 1H), 2.12 (s, 2H),2.02 (br. s, 5H), 1.94 (br.s, 4H), 1.87-1.66 (br. m, 3H), 1.65-1.55 (br.s, 4H), 1.43-1.30 (br.s, 3H), 1.30-1.15 (Br. m, 7H), 1.07-0.98 (m, 3H),0.897 (br. s, 12H). ³¹P NMR (toluene-ds, d, ppm): 25.6 (s).

Preparation ofDibenzyl(pentamethylcyclopentadienyl)(1-adamantyl)bis(3,5-dimethyl-1-adamantyl)phosphiniminateZirconium, Cp*[(1-Ad)(3,5-Me2-1-Ad)₂PN]Zr(CH₂Ph)₂

A solution of Cp*[(1-Ad)(1-Ad′₂)PN]ZrCl₂ (1.29 g, 1.604 mmol) in toluene(30 mL) was chilled in a -35° C. freezer for 0.5 hours. PhCH₂MgCl inEt₂O (1 M, 3.7 mL) was added to the solution. The mixture was stirredovernight and was filtered. The filtrate was pumped to dryness andtoluene (10 mL) was added to dissolve the solid. A small amount of solidwas filtered off and the filtrate was pumped to dryness again. Pentane(~10 mL) was added to dissolve the solid. The turbid pentane solutionwas filtered off to remove solid and the clear filtrate was pumped toabout 5 mL. Product did not crystallize at -35° C. The solution waspumped to make sure all toluene was removed. The solid (1.20 g) was verysoluble in pentane. ¹H NMR (toluene-ds, d, ppm): 7.21-6.82 (m, 10H),2.57-2.32 (br. s, 8H), 2.29-2.17 (m, 7H), 2.16-2.13 (br.m, 3H), 2.12 (s,2H), 2.06-2.01 (br. s, 5H), 1.97 (s, 15H), 1.95-1.90 (br. s, 3H),1.84-1.55 (br. m, 7H), 1.48-1.14 (br.m, 12H), 1.06-0.99 (m, 3H),0.94-0.84 (br.s, 12H). ³¹P NMR (toluene-ds, d, ppm): 21.3 (s).

Preparation of(pentamethylcyclopentadienyl)(1-adamantyl)bis(3,5-dimethyl-1-adamantyl)phosphiniminateHafnium Dichloride, Cp*[(1-Ad)(3,5-Me₂-1-Ad)₂PN]HfCl₂

nBuLi (1.6 M, 1.35 mL, 2.16 mmol) was added to a toluene solution (30mL) of (1-Ad)(1-Ad′₂)P=NH (1.00 g, 1.97 mmol) at room temperature. Thesolid dissolved very quickly after the addition. The solution wasstirred for 2 hours and was added to a slurry of Cp*HfCl₃ (0.838 g, 1.97mmol) in toluene (40 ml) at -70° C. The resulted clear solution wasallowed to warm to room temperature and was stirred over a weekend. Thecloudy solution was filtered to remove the fine solid and the filtratewas pumped to dryness. The residue was thoroughly extracted with pentane(3×10 mL). A small amount of pentane insoluble solid was found to be theligand (1-Ad)(1-Ad′₂)P=NH. The pentane solution was pumped to dryness.¹H NMR (toluene-ds, d, ppm): 2.7-2.3 (v.br. s, 8H), 2.26 (s, 15H), 2.03(br.s, 5H), 1.94 (br.s, 5H), 1.63-1.69 (v. br, 3H), 1.61 (br.d., 4H),1.43-1.13 (br. m, 13H), 1.02 (br.d, 3H), 0.90 (multiple s, 12H). ³¹P NMR(toluene-d₈, d, ppm): 29.2 (s).

Preparation ofDibenzyl(pentamethylcyclopentadienyl)(1-adamantyl)bis(3,5-dimethyl-1-adamantyl)phosphiniminateHafnium, Cp*[(1-Ad)(3,5-Me₂-1-Ad)₂PN]Hf(CH₂Ph)₂

The solid from the above reaction was dissolved in toluene (35 mL).PhCH₂MgCl (1.0 M in diethyl ether, 7 mL) was added. The mixture wasstirred overnight and was pumped to dryness. The foamy solid wasextracted with pentane (150 mL). The pentane solution was filtered, andthe volume was reduced to about 50 mL by vacuum pumping. The turbidsolution was filtered, and the clear filtrate was pumped to dryness. Thesolid was re-dissolved in pentane. Some small amount of solid did notdissolve, which was filtered off. The filtrate was pumped to dryness togive 1.47 g of product. ¹H NMR (toluene-d₈, d, ppm): 7.24-7.10 (m, 7H).6.92-6.84 (m, 2H), 6.80-6.70 (m, 1H), 2.60-2.32 (br.s, 6H), 2.23 (m,5H), 2.06-2.01 (br.s, 4H), 1.99 (s, 15H), 1.96-1.89 (br.m, 4H),1.78-1.67 (br.m, 5H), 1.66-1.57 (br.m, 4H), 1.44-1.26 (br.m, 9H),1.26-1.16 (br.d, 5H), 1.07-1.0 (br.d, 3H), 0.89 (slightly br.s, 12H).³¹P NMR (toluene-d₈, d, ppm): 26.2 (s).

Preparation ofDibenzyl(pentamethylcyclopentadienyl)(tri(1-adamantyl)phosphiniminate)zirconium, Cp*(1-Ad₃PN)ZrBn₂

A toluene solution of Cp*Zr(CH₂Ph)₃ in a 20 mL hypo vial was added to aslurry of 1-AdsP=NH in toluene (~15 mL) in a 100 mL Schlenk flask at-70° C. The hypo vial was rinsed with toluene (2×3 mL) and the rinsingsolution was added to the Schlenk flask. The reaction mixture wasallowed to warm to room temperature with the cold bath and was stirredovernight. The solution was pumped to dryness. ¹H NMR showed smallamount of Cp*Zr(CH₂Ph)₃ in addition to the product (from the peak of Cp*methyl signal). ³¹P NMR showed a singlet (product) and a very smallamounts of impurities. The solid was re-dissolved in toluene and thevolume of the solution was reduced to about 5 mL by vacuum pumping.Pentane (5 mL) was added dropwise to the toluene solution which was putin a -35° C. freezer. Product did not crystallize. More pentane (~5 mL)was added to the solution and the solution was again put in the freezerovernight. Product crystallized. The mother liquor was separated. Thesolid was washed with pentane (2x5mL) and was dried under vacuum (0.45g). ¹H NMR (toluene-ds, d, ppm): 7.19-7.11 (m, 8H), 6.87-6.81 (m, 2H),2.38-2.23 (m, 22H), 1.99 (s, 15H), 1.94 (br.s, 10H), 1.81-1.67 (br. m,9H), 1.66-1.59 (br.d, 10H). ³¹P NMR (toluene-ds, d, ppm): 22.3 (s).

Preparation of2,3,4,5-tetramethyl[1-(3,5-di-tert-butyl)]cyclopentadiene,3,5-tBu2Ph-Me₄CpH

1-bromo-3,5-di-tbutylbenzene (2.69 g, 10 mmol) in THF (10 mL) was addedin small portions to a 350 mg of activated magnesium turnings (14.6mmol) in THF (3 mL). Reaction started in about 5 minutes as the color ofthe solution turned to a tint of brown. THF (~15 mL) was added to thereaction flask and the remaining 1-bromo-3,5-di-tert-butylbenzene in THFwas added gradually. The reaction temperature was maintained at 50° C.and was stirred for 6 hours to afford the Grignard reagent. The solutionwas filtered to remove unreacted magnesium (which was disposed aspyrophoric solid) and the filtrate was added to a THF solution (30 mL)of 1,2,3,4-trtramethylcyclopenten-1-one. After being stirred at roomtemperature for 1 hour, the reaction solution was heated at 70°overnight. The solution was cooled to room temperature and was added toa stirred HCl aqueous solution (15 mL). After one hour, the product wasworked up with diethyl ether extraction to afford 2.8 g of the3,5-di-t-butylpheny-tetramethylcycloentadiene isomers.

Preparation of2,3,4,5-tetramethyl[1-(3,5-di-tert-butylphenyl)]cyclopentadienyl hafniumtrichloride, (2,3,4,5-Me₄)(3,5-tBu₂Ph)CpHfCl₃

3,5-di-t-butylpheny-tetramethylcycloentadiene (3.50 g, 10.8 mmol) wasweighed in a 100 mL round bottomed flask in a glove box. Diethyl ether(50 mL) was added. Benzyl potassium (1.406 g, 10.8 mmol) was added insmall portions to the solution. Immediate precipitate was observed.After stirring the reaction for 1.5 hours, the slurry was filtered toremove any diethyl ether-soluble by-products. The solid was rinsed withdiethyl ether (2×5 mL) and pentane (10 mL) and was dried under vacuum.The solid was dissolved in THF (30 mL) and Me₃SiCl (2.0 g, 18.4 mmol)was added. The solution was stirred overnight and was pumped to dryness.Note: KCl dissolved in the product. Pentane (30 mL) was added to theliquid, lots of precipitate (KCl) was observed, which was filtered offand the pentane filtrate was pumped to dryness to give a viscous oil of3,5-tBu₂Ph-Me₄Cp-SiMe₃.

The product from the previous reaction (1.015 g, 2.652 mmol) wasdissolved with heptane (~20 mL). The solution was added to a 100 mLround bottomed flask with HfCl₄ (0.860 2.68 mmol). The slurry was heatedto 70° C. overnight. The white slurry changed to almost homogeneous dullred solution. Heptane was removed by vacuum pumping and the solid wasextracted with pentane (30 mL). The pentane solution was filtered toremove a small amount of solid and the filtrate was reduced to about 3mL. Product crystallized at -35° C. overnight (1.173 g). ¹H NMR(toluene-ds, d, ppm): 7.50 (s, 1H), 7.32 (s, 2H), 2.25 (s, 6H), 2.00 (s,6H), 1.32 (s, 18H).

(2,3,4,5-Tetramethyl[1-(3,5-di-tert-butylphenyl)lcyclopentadienyl)(tri(1-adamantyl)phosphiniminate)Hafnium Dichloride, (3,5-tBu₂Ph-Me₄Cp)(1-Ad₃PN)HfCl₂

A solution of (3,5-tBu₂Ph-Me₄Cp)HfCl₃ (1.934 g, 3.25 mmol) in toluene(30 mL) was added to a slurry of (1—Ad)₃P═NLi (1.48 g, 3.25 mmol) intoluene (30 mL) at-70° C. The slurry was stirred at -70° C. for 5minutes and the cold bath was removed. The reaction was stirred at roomtemperature for 24 hours. The solution was filtered to remove LiCl andthe filtrate was concentrated by vacuum pumping to about 2 mL. 2 mL ofpentane was added dropwise. The solution was left in a -35° C. freezerovernight and the product crystallized. The mother liquor was pipettedout. The solid was washed with cold toluene (-35° C., 2×5 mL), then withpentane (1×10 mL) and was dried under vacuum. 2.50 g of very crystallinesolid was obtained. ¹H NMR (toluene-d₈, d, ppm): 7.61 (s, 2H), 7.40 (s,1H), 2.53 (s, 6H), 2.28 (s, 6H), 2.47-2.18 (v.br s, 18H), 1.87 (br.s,10H), 1.77-1.53 (m, 17H), 1.39 (s, 18H). ³¹P NMR (toluene-d₈, d, ppm):29.4 (s).

Dimethyl(2,3,4,5-tetramethyl[1-(3,5-di-tert-butylphenyl)]cyclopentadienyl)(tri(1-adamantyl)phosphiniminate)hafnium, (3,5-tBu₂Ph-Me₄Cp)(1-Ad₃PN)HfMe₂

(3,5-tBu₂Ph-Me₄Cp)(1-Ad₃PN)HfCl₂ (0.907 g, 0.9 mmol) was dissolved intoluene (125 mL). To this solution was added CH₃MgBr solution (3 M inEt₂O, 1.4 mL). After stirring the reaction mixture for 2 hours, thesolution became turbid. Stirring continued overnight. The solution waspumped to remove diethyl ether and was filtered to remove the suspendedsolid. The filtrate was pumped to dryness. Toluene (50 mL) was added todissolve the product. The solution was filtered to remove a small amountof solid and the filtrate was pumped to dryness. The above process wasrepeated. Crystalline solid (0.460 g) was obtained after the solutionwas pumped to dryness. ¹H NMR (toluene-d₈, d, ppm): 7.42 (br.s, 3H),2.42 (s, 6H), 2.40 (br.s, 16H), 1.93 (br. 9H), 1.87 (br. m, 10H), 1.64(dr.d, 10H), 1.41 (s, 18H), 0.19 (s, 6H). ³¹P NMR (toluene-d₈, d, ppm):24.9 (s).

Preparation of Trans-2-methyl-2-butenoyl Chloride

A solution of oxalyl chloride (6.47 g, 51 mmol) in CH₂Cl₂ (40 mL) wasadded dropwise through a 20-gauge cannula to a solution oftrans-2-methyl-2-butenoic acid (5.005 g, 50 mmol) in CH₂Cl₂ (30 mL). Theaddition took 20 minutes. Gas evolution was observed, which was ventedout through a 20-gauge cannula on the septum to a sodium hydroxidesolution (4 M, ~200 mL). The reaction became cloudy, which was stirredovernight while a steady small stream of nitrogen flowed through theseptum to the top of the reaction flask then out through a 20-gaugecannula to the sodium hydroxide solution. The CH₂Cl₂ was carefullydistilled out from the reaction flask. Pentane (30 mL) was added to theflask to dissolve the product. The undissolved solid (the startingmaterial) was filtered off. Pentane was removed by distillation from thefiltrate. The product was a clear liquid (which was used for the nextreaction without being weighed). ¹H NMR (toluene-d₈, d, ppm): 6.86 (qq,J₁= 7.0 Hz, J₂= 1.3 Hz), 1.45 (pentet, J = 1.1 Hz, 3H), 1.18 (dq, J₁ =7.0 Hz, J₂ = 1.3 Hz).

Preparation of1,4-Dihydro-1,2-dimethyl-4-phenylcyclopent[b]indol-3(2H)-one

N-Phenylindole (8.503 g, 44 mmol) prepared by the method reported inSyn. Lett. 2019, 30(11), 1313-1316 was dissolved in THF (150 mL). nBuLi(1.6 M, 28.3 mL) was very slowly added in 2 hours to this solutionmaintained at -13° C. with an ethanol/dry ice bath. The cold bath wasremoved, and the reaction was stirred for 15 minutes and then cooled to-30° C. with an ethanol/dry ice bath. A THF solution (80 mL) of ZnCl₂was added. The solution was stirred and warmed to room temperature in 40minutes.

A solution of Pd(PPh₃)₄ (1 mmol%, 0.51 g) in THF (30 mL) was addedthrough a cannula followed with adding trans-2-methyl-2-butenoylchloride (5.34 g, 45 mmol). The mixture was stirred overnight and waspumped to dryness. The reaction residue was extracted with diethyl ether(4x200 mL) and the diethyl ether solution was washed with saturated NaClsolution (3x50 mL). The diethyl ether solution was dried with anhydrousMgSO₄ and was pumped to remove volatiles to give a thick oil.

The thick oil was dissolved in CH₂Cl₂ (800 mL) and 0.260 g of CF₃SO₃Hwas added in 10 mL of CH₂Cl₂. The reaction was stirred for 1.5 hours andthe CH₂Cl₂ removed by using a rotovap. The thick oil thus obtained wasdissolved in pentane/diethyl ether (10:1, 200 mL). The solution waspassed through an 18″ column of alumina (f=0.5″) and the column wasflushed with additional 600 mL of the mixed solvents. The volatiles fromthe filtrate were removed using a rotavap to give an orange oil. ¹H NMRshowed it was 100% pure (two isomers ~1:0.5 ratio, 11.0 g). ¹H NMR(toluene-d₈, d, ppm): 7.72-7.64 (m, 1.5H), 7.49 (7.35 (m, 8H), 7.32-7.2(m, 3H), 7.16-7.08 (m, 2H), 7.08-7.01 (m, 0.5H), 3.58 (pentet, J = 7 Hz,0.5H), 3.08 (pentet, 0.5H), 3.02 (dq, J₁ = 7 Hz, J₂ = 2.5 Hz, 1H), 2.48(dq, J₁ = 7 Hz, J₂ = 2.5 Hz, 1H), 1.47 (d, J = 7 Hz, 3H), 1.31 (d, J = 7Hz, 1.5H), 1.26 (d, J = 7 Hz, 3H), 1.16 (d, J = 7 Hz, 1.5H).

Preparation of 1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole

CH₃MgCl in THF (3.0 M, 10 mL) was added to a solution1,4-Dihydro-1,2-dimethyl-4-phenylcyclopent[b]indol-3(2H)-one (5.42 g,19.68 mmol) in THF (100 mL). The reaction was heated to 58° C.overnight. Lots of solid precipitated. The slurry was carefully pipettedto a 150 mL of aqueous HCl (total amount of HCl, 100 mmol) and thesolution was stirred for 2 hours. The organic phase was separated, andthe aqueous layer was extracted with diethyl ether (3×50 mL). Thecombined organic phases were washed with saturated NaCl solution (80mL), dried with anhydrous MgSO₄ and was pumped to dryness. The thick oilwas dissolved in pentane (~100 mL), the solution was passed through analumina column (12″, f=0.5″) and was rinsed with 400 mL of pentane. Thefiltrate was evaporated to dryness producing a light orange oil (4.77g). Note: The product decomposes in CDCl₃ and with dry HCl. ¹H NMR(acetone-d₆, d, ppm): 7.65-7.57 (m, 3H), 7.57-7.48 (m, 4H), 7.13-7.10(m, 1H), 7.09-7.05 (m, 1H), 6.98-6.93 (m, 1H), 2.00 (s, 3H), 1.68 (s,3H), 1.38 (d, J = 7 Hz, 3H).

Preparation of1,2,3-trimethyl-1-trimethylsilyl-4-phenyl-4-hydrocyclopent[b]indole

To a stirred solution of1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole (2.217 g, 8.11mol) in diethyl ether (35 mL) was added benzyl potassium (1.06 g, 8.11mmol). The yellow orange slurry gradually became red and benzylpotassium gradually slowly disappeared. In about 40 minutes, all thebenzyl potassium disappeared. The solution became turbid and red solidformed. The slurry was stirred for 2.5 hours and was pumped to dryness.The solid was washed with pentane. The solid was dissolved in THF (40mL) to form a very dark red solution. MesSiCl (1.2 g, 11 mmol, excess)in THF (10 mL) was added to the above solution. The dark colordisappeared to became almost colorless. The solution was left stirringovernight and was pumped to dryness. The residue was extracted withpentane (50 mL) and the pentane solution was pumped to dryness to givethe target product as a colorless oil (without weighing, used in thenext step). ¹H NMR (CD₂Cl₂, d, ppm): 7.58-7.52 (m, 3H), 7.47-7.40 (m,3H), 1.21-7.17 (d, J = 7 Hz, 1H), 7.07 (t, J = 7 Hz, 1H), 7.01-6.96 (m,1H), 2.00 (s, 3H), 1.72 (s, 3H), 1.58 (s, 3H), 0.05 (s, 9H).

Preparation of1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolylhafnium Trichloride

To 1,2,3-trimethyl-1-trimethylsilyl-4-phenyl-4-hydrocyclopent[b]indoleprepared in the last step in a 100 mL round bottomed flask was dissolvedin toluene (40 mL). HfCl₄ (2.6 g, 8.1 mmol) was added to the flask froma hypo vial. The mixture was heated to 90° C., the solution becameorange and the HfCl₄ started to dissolve. After 0.5 hours, all HfCl₄dissolved. The mixture was stirred at 79° C. overnight. Pumped offtoluene, and the residue was extracted with dichloromethane (80 mL).Attempt to crystallize the product failed. Solvent was pumped to drynessand 3.0 gram of orange solid was obtained. ¹H NMR showed it is thedesired crude product.

Dimethyl(1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyi)(tri(1-adamantyl)phosphiniminate)Hafnium

To the orange solid from the last step (2.0 g, 3.58 mmol) in toluene(~40 mL) at-70° C. was added a slurry of (1—Ad)₃P═NLi prepared fromadding nBuLi (2.28 mL) to (1—Ad)₃P═NH (1.62 g, 3.58 mmol) in toluene (30mL) and overnight stirring. The mixture was stirred and was allowed towarm to room temperature. After being stirred overnight, the solutionwas filtered to remove LiCl through celite. This forms the[1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl](tri-1-adamantyl)hafniumdichloride. The solution was pumped to dryness and was used for the nextstep.

MeMgBr (3.0 M, 3.0 mL) in diethyl ether was added to a toluene solutionof the solid from the last step. The solution was stirred overnight andwas pumped to dryness. The residue was extracted with pentane (~150 mL).The pentane extract was filtered to remove insoluble solids. The pentanefiltrate was concentrated to 25 mL and cooled at -35° C.; however, nocrystals formed. However, once the solution warmed to room temperatureand allowed to stand for about 30 minutes, the product began tocrystallize. After 3 hours, the mother liquor was decanted and the whitecrystalline solid was washed with pentane (3×5 mL) and dried undervacuum (0.63 g). ¹H NMR (toluene-d₈, d, ppm): 7.85-7.78 (m, 1H), 7.51(d, J = 7 Hz, 2H), 7.33-7.28 (m, 1H), 7.19 (t, J = 7 Hz, 2H), 7.15-7.06(m, 2H), 7.06-7.0 (m, 1H), 2.66 (s, 3H), 2.40-2.29 (br.s, 18H), 2.28 (s,3H), 2.18 (s, 3H), 1.92 (br.s, 9H), 1.79 (-1.55(m, 18H), -0.120 (s, 3H),-0.229 (s, 3H). ³¹P NMR (toluene-ds, d, ppm): 24.78 (s).

An alternate higher yield synthesis ofdimethyl(1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl)(tri(1-adamantyl)phosphiniminate)hafnium follows.

Preparation of1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolylhafnium Trichloride

nBuLi (1.6 M, 3.17 mL) was added to a solution of1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole (1.389 g, 5.08mmol) in diethyl ether (60 mL) in a 125 mL hypo vial at roomtemperature. A very thick slurry formed, which was stirred at roomtemperature for 1 hour. HfCl₄ (1.627 g, 5.08 mmol) was weighed in a 300mL Kontes flask and toluene (25 mL) was added. The flask was cooled to-70° C. and the content was stirred. Diethyl ether (~100 mL) was addedslowly. The very thick slurry from the last reaction was transferred tothe Schlenk flask. The vial was rinsed with diethyl ether (3×5 mL) andthe washing solution was transferred to the Schlenk flask. The cold bathwas removed, and the reaction was allowed to warm to room temperature.No apparent change was observed. The content was stirred for 3 days. Ayellow solution formed with suspension of LiCl. Diethyl ether wasremoved by vacuum pumping leaving a toluene solution of the product withlittle amount of LiCl. The product was used without further isolation.

Preparation of[1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl](tri(1-adamantyl)phosphiniminate) Hafnium Dichloride

nBuLi (1.6 M, 3.33 mL) was added to (1—Ad)₃P═NH (2.294 g, 5.08 mol) intoluene (~ 40 mL) at room temperature. The mixture was stirred at roomtemperature for 3 hours to form a slurry of (1—Ad)₃P═NLi in toluene.This slurry was transferred to the Cp′HfCl₃ solution at -70° C. Thestirred slurry was warmed to room temperature. After being stirredovernight, the solid was filtered off and the filtrate was pumped todryness. ¹H and ³¹P NMR showed that the product (Cp′)[(1-Ad)₃PN]HfCl₂was pure. ¹H NMR (CD₂Cl₂, d, ppm): 7.77 (d, J = 7 Hz, 1H), 7.67 (br.d, J= 7 Hz, 2H), 7.54 (t, J = 8 Hz, 2H), 7.41 (tt, J = 7 Hz, J = 1.3 Hz,1H), 7.25 (d, J = 7 Hz, 1H), 7.20 (td, J = 7 Hz, J = 1.3 Hz, 1H), 7.11(td, J = 7 Hz, J = 1.3 Hz, 1H), 2.79 (s, 3H), 2.40 (s, 3H), 2.32 (br.s,16H), 2.11 (s, 3H), 2.02 (br.s, 9H), 1.76 (br.m, 20H). ³¹P NMR (CD₂Cl₂,d, ppm): 30.9 (s).

PreparationDimethyl(1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl(tri,1-Adamantyl)Phosphiniminate) Hafnium

To the solution of the above reaction at room temperature was addedCH₃MgBr solution (3.0 M, 3.0 mL) in diethyl ether. The solution wasstirred overnight and was pumped to dryness. The solid was extractedwith pentane (3×80 mL). The pentane solution was pumped to dryness togive the target product (1.12 g). ¹H NMR (toluene-ds, d, ppm): 7.83-7.78(m, 1H), 7.51 (d, J = 7 Hz, 2H), 7.33-7.27 (m, 1H), 7.19 (t, J = 7 Hz,2H), 7.15-7.06 (3, 2H), 7.06-7.0 (m, 1H), 2.66 (s, 3H), 2.40-2.29 (br.s,18H), 2.28 (s, 3H), 2.18 (s, 3H), 1.92 (br.s, 9H), 1.79 (-1.55 (m, 18H),-0.127 (s, 3H), -0.233 (s, 3H). ³¹P NMR (toluene-d₈, d, ppm): 24.84 (s).

1-Pentafluorobenzyl-2,3,4,5-tetramethylcyclopentadiene

1,2,3,4-Tetramethl-1,3-cyclopentadiene (2 g, 16.37 mmol) was dissolvedin the mixture of toluene (25 mL) and THF (25 mL). KN(TMS)₂ (3.27 g,16.39 mmol) was added as a solid at room temperature. The mixture wasstirred at room temperature for at least 3 hours, and it was then addedinto a THF (80 mL) solution of 2,3,4,5,6-pentafluorobenzyl bromide (4.30g, 16.35 mmol) dropwise at -78° C. The reaction was warmed to roomtemperature and stirred overnight. All volatiles were removed in vacuo,and the product was extracted with toluene (3×50 mL) and filteredthrough a pad of Celite. The solvent of the combined filtrate wasremoved under vacuum, and the product was obtained as a yellow liquid(4.5 g).

1-Pentafluorobenzyl-1-trimethylsilyl-2,3,4,5-tetramethyl-cyclopentadiene

The yellow liquid (4.5 g) from above was dissolved in toluene (80 mL),and a toluene solution of KN(TMS)₂ (3 g, 15.04 mmol) was added dropwiseat room temperature. The reaction was stirred overnight. The precipitate(4 g) was collected through filtration, washed with pentane (3×5 mL),and dried in vacuo. The dried precipitate was dissolved in THF (60 mL)and chlorotrimethylsilane (3.52 g, 17.64 mmol) was added at roomtemperature. The reaction was stirred overnight. All volatiles wereremoved in vacuo, and the product was extracted with toluene (350 mL).After filtration, the solvent of the combined filtrate was removed underreduced pressure to give the product as a yellow liquid (2.5 g).

Tribenzyl(1-pentafluorobenzyl-2,3,4,5-tetramethyl-cyclopentadienide)Hafnium

The product obtained from above (2.5 g), HfCl₄ (2.14 g, 6.68 mmol) andtoluene (50 mL) was mixed and heated at 90° C. overnight. All solidsdissolved and a clear purple solution was obtained. After all volatileswere removed in vacuo, the residue was dissolved in toluene (50 mL).Benzylmagnesium chloride (14.6 mL, 14.6 mmol, 1 M in Et₂O) was added atroom temperature. The reaction was stirred overnight, and all volatileswere removed in vacuo. Toluene (20 mL) was added into the residue. Afterbeing stirred for 20 minutes, all volatiles were removed under vacuumagain. This process was repeated 3 times. The product was then extractedwith toluene (3×50 mL) and filtered through a pad of Celite. After allsolvents of the combined filtrate were removed, a yellow oil wasobtained. The oil was dissolved in heptane (15 mL). The product wasobtained as yellow crystals after the heptane solution was placed at-35° C. for several days. Yield: 4.9 g. ¹H NMR (toluene-d₈, δ, ppm):7.30 (t, 6H), 7.07 (d, 3H), 6.80 (d, 6H), 3.55 (s, 2H), 2.05 (s, 6H),1.95 (s, 6H), 1.86 (s, 6H). ¹⁹FNMR (toluene-d₈, δ, ppm): -140.64 (d,2F), -156.42 (t, 1F), -161.59 (dt, 2F).

Dibenzyl(1-pentafluorobenzyl-2,3,4,5-tetramethyl-cyclopentadienide)(tri(1-adamantyl)phosphiniminate)hafnium

Tribenzyl, (1-pentafluorobenzyl-2,3,4,5-tetramethyl-cyclopentadienide)hafnium (2.3 g, 3.05 mmol) was dissolved in toluene (50 mL).Tri(1-adamantyl)phosphinimine (1.38 g, 3.05 mmol) was added as a solid.The mixture was stirred at room temperature for 3 hours. A clean yellowsolution was formed. All volatiles were removed to give the desiredproduct. The analytical pure product was obtained as a white solid fromrecrystallization in a toluene/heptane solution at -35° C. Yield: 2.7 g,80%. ¹H NMR (bromobenzene-d₅, δ, ppm): 7.35 (t, 4H), 7.29 (d, 4H), 7.00(t, 2H), 3.82 (s, 2H), 2.53 (br, 18H), 2.26 (s, 4H), 2.23 (s, 6H), 2.17(br, 9H), 2.12 (s, 6H), 1.94 (d, 9H), 1.83 (d, 9H). ³¹P NMR(bromobenzene-d₅, δ, ppm): 28.34 (s). ¹⁹F NMR (bromobenzene-d₅, δ, ppm):-140.68 (dd, 2F), -157.74 (t, 1F), -162.24 (dt, 2F).

Preparation of Potassium 1,2,3,4,5-pentapropylcyclopentadienide

1,2,3,4,5-pentapropylcyclopentadiene (6.2 g, 22.4 mmol), preparedaccording to the procedure described in Chemistry - A European Journal2002, 8(18), 4292-4298, was dissolved in toluene (20 mL). Potassiumhexamethyldisilazide (4.483 g, 22.5 mmol) was dissolved in toluene (40mL) and added and the mixture stirred overnight, resulting in aprecipitate. The solids were collected, rinsed with toluene (2×10 mL),pentane (3×10 mL) and dried under reduced pressure. The product was usedas is.

Preparation ofTrimethyl(1,2,3,4,5-pentapropylcyclopenta-2,4-dien-1-yl)silane

Potassium 1,2,3,4,5-pentapropylcyclopentadienide (0.749 g, 2.38 mmol)was slurried in THF (5 mL) in a vial. On vigorous stirring,chlorotrimethylsilane (0.33 mL, 2.62 mmol) was added. The reactionmixture was stirred overnight, resulting in a thickened creamy yellowsuspension. Volatiles were removed, yielding a paste. Extraction withpentane and filtration afforded a yellow filtrate. Evaporation of thefiltrate afforded the desired product as a yellow oil (0.602 g, 1.73mmol, 73% yield). ¹H NMR (toluene-ds, 5, ppm): 2.50 - 2.10 (br, 10H,CH₂CH₂CH₃), 1.80 - 1.40 (br, 10H, CH₂CH₂CH₃), 1.10 - 0.80 (br, 15H,CH₂CH₂CH₃), 0.00 (s, 9H, SiMe₃).

Preparation of (pentapropylcyclopentadienyl)hafnium Trichloride

Trimethyl(1,2,3,4,5-pentapropylcyclopenta-2,4-dien-1-yl)silane (1.969 g,5.647 mmol) was diluted with toluene (50 mL) in a 10-mL round-bottomedflask. Hafnium(IV) chloride (2.713 g, 8.470 mmol) was added, a condenserattached, and the reaction mixture was heated to 95° C. for 3 days. Thedark red-brown mixture was filtered, and the filtrate was evaporated todryness. The crude product was purified by recrystallization fromtoluene/heptane to afford the desired product as a dark brown solid(2.353 g, 74% yield). ¹H NMR (toluene-d₈, δ, ppm): 2.60 (t, 10H,CH₂CH₂CH₃), 1.40 (sextet, 10H, CH₂CH₂CH₃), 0.87 (t, 15H, CH₂CH₂CH₃).

Preparation of Tribenzyl(pentapropylcyclopentadienyl)hafnium

(Pentapropylcyclopentadienyl)hafnium(IV) chloride (1.723 g, 3.075 mmol)was dissolved in toluene (12 mL). On vigorous stirring, benzylmagnesiumchloride (12.30 mL of 1.0 M solution in Et₂O, 12.30 mmol) was added,resulting in a bright yellow suspension. After stirring for 4 hours,volatiles were evaporated under reduced pressure to afford a sticky gel.Trituration with pentane afforded a solid residue. The residue wasextracted with toluene and filtered. The filtrate was evaporated,slurried in heptane, and solids were collected and dried to afford thedesired product as bright yellow solids (0.969 g, 43% yield). ¹H NMR(toluene-d₈, δ, ppm): 7.17 (t, 6H, m-ArH), 6.91 (t, 3H, p-ArH), 6.74 (d,6H, o-ArH), 2.30 (m, 10H, CH₂CH₂CH₃), 1.85 (s, 6H, CH₂Ph), 1.55 (sextet,10H, CH₂CH₂CH₃), 0.98 (t, 15H, CH₂CH₂CH₃).

Preparation ofDibenzyl(pentapropylcyclopentadienyl)(tri(1-adamantyl)phosphiniminate)Hafnium

Tribenzyl(pentapropylcyclopentadienyl)hafnium(IV) (1.061 g, 1.459 mmol)and tri(1-adamantyl)phosphinimine (0.659 g, 1.459 mmol) were slurried intoluene (15 mL) and stirred overnight. The mixture was diluted withtoluene (50 mL), filtered, and the filtrate was concentrated tosaturation at 60° C., cooled to room temperature, and layered withpentane. Recrystallized product was recovered the next day (0.644 g, 41%recrystallized yield). ¹H NMR (toluene-d₈, δ, ppm): 7.30-6.80 (m, 10H,CH₂Ph), 2.60-1.50 (m, 54H, CH₂CH₂CH₃ & 1-Ad), 1.06 (t, 15H, CH₂CH₂CH₃).

Preparation ofDibenzyl(cyclopentadienyl)(tri(1-adamantyl)phosphiniminate) Zirconium

Cyclopentadienylzirconium(IV) trichloride (0.672 g, 2.56 mmol) wasslurried in Et₂O (40 mL) and cooled to -30° C. Methylmagnesium bromide(2.84 mL of 3.0 M solution in Et₂O, 8.52 mmol) was added, affording acreamy yellow suspension. After stirring for 3 hours at -30° C.,(1-Ad)₃PNH was added. The reaction mixture was warmed to roomtemperature overnight. Volatiles were removed, the residue extractedwith toluene, filtered, and the filtrate was evaporated under reducedpressure. Repeated recrystallizations from chlorobenzene and pentaneafforded the desired product as a white solid (0.31 g, 19%recrystallized yield). ¹H NMR (toluene-ds, δ, ppm): 6.38 (s, 5H, C₅H₅),2.41 (br, 18H, 1-Ad), 1.96 (br, 9H, 1-Ad), 1.90-1.50 (m, 18H, 1-Ad),0.33 (s, 6H, ZrMe₂). ³¹P{¹H} NMR (toluene-d₈, δ, ppm): 18.5 (s).

Continuous Solution Polymerization

Continuous polymerizations were conducted on a continuous polymerizationunit (CPU) using cyclohexane as the solvent. The CPU contained a 71.5 mLstirred reactor and was operated between 130 to 190° C. for thepolymerization experiments. An upstream mixing reactor having a 20 mLvolume was operated at 5° C. lower than the polymerization reactor. Themixing reactor was used to preheat the ethylene, octene and some of thesolvent streams. Catalyst feeds (xylene or cyclohexane solutions of thepre-catalyst complex ((e.g., Cp*(1-Ad₃PN)HfCl₂)) and (Ph₃C)[B(C₆F₅)₄] asa catalyst activator and additional solvent were added directly to thepolymerization reactor in a continuous process. Additional feeds ofMMAO-7 with and without 2,6-di-tert-butyl-4-ethylphenol (BHEB) andsolvent were also added to the polymerization reactor in a continuousprocess. Note that MAO refers to MMAO-7; MMAO-7 is a commerciallyavailable methylaluminoxane that is reported to contain some higheralkyl substituents (C₄-C₆) in addition to methyl substituents. A totalcontinuous flow of 27 mL/min into the polymerization reactor wasmaintained.

Copolymers were made at 1-octene / ethylene weight ratios ranging from0.15 to 0.5. The ethylene was fed at a 10 wt% ethylene concentration inthe polymerization reactor. The CPU system operated at a pressure of10.5 MPa. The solvent, monomer, and comonomer streams were all purifiedby the CPU systems before entering the reactor. The polymerizationactivity, k_(p) (expressed in mM⁻¹·min⁻¹), is defined as:

$k_{\text{p}} = ( \frac{Q}{100 - Q} )( \frac{1}{\lbrack M\rbrack} )( \frac{1}{\text{HUT}} )$

where Q is ethylene conversion (%) (measured using an online gaschromatograph (GC)), [M] is catalyst concentration in the reactor (mM),and HUT is hold-up time in the reactor (2.6 min).

Copolymer samples were collected at 90±1 % ethylene conversion (Q),dried in a vacuum oven, ground, and then analyzed using FTIR (forshort-chain branch frequency) and GPC-RI (for molecular weight anddistribution). Polymerization results are summarized in Tables 1-3below.

Polymerization Results

The results shown in Table 1 are all comparative (Comparative Examples 1through 7) because the phosphinimine ligand of the catalyst used inthese experiments does not have an adamantyl moiety.

TABLE 1 Impact of Scavenger on Cp*(tBu₃PN)Hf(CH₂Ph)₂ Catalyst¹ Examples(Comparative) Temp. (°C) Scavenger Al/Hf (mol/mol) BHEB/Al (mol/mol)Activity k_(p) Ethylene Conversion % Comp. 1 160 MAO/BHEB 39.75 0.305936 89.14 Comp. 2 160 MAO/BHEB 37.50 0.30 6106 89.41 Comp. 3 160 MAOonly 18.00 - 3280 90.43 Comp. 4 140 TIBAL 9.00 - 1327 88.43 Comp. 5 160TEAL 37.5 - 45 5.81 Comp. 6 190 TEAL 4.78 - 7 7.3 Comp. 7 190 TEAL14.34 - 10 9.9 Note 1: The 1-Octene/ethylene ratio was 0.3 wt/wt forExamples 1-5; no 1-octene was added to thereactor for Examples 6-7. The(Ph₃C)[B(C₆F₅)₄]/Hf molar ratio was 1.2 for Examples 1-5 and 2.0 forExamples 6-7; TIBAL = triisopropyl aluminum; TEAL = triethyl aluminum;BHEB = 2,6-di-tert-butyl-4-ethylphenol; Cp* =pentamethylcyclopentadienyl.

Comparative Examples 1 and 2 show that the catalystCp*(tBu₃PN)Hf(CH₂Ph)₂ had moderate activity (k_(p) of 5936 and 6106respectively) at 160° C. when MAO/BHEB was used a scavenger. When BHEBwas removed while using MAO as the scavenger, as was done in Comp.Example 3, the activity drastically dropped to a k_(p) of 3280. Whensimple aluminum alkyls (TIBAL, TEAL) were used as scavengers (Comp.Examples 4-7), the catalyst had low activity or almost no activity atboth 160° C. and 190° C.

TABLE 2 Polymerization Results with Cp*(1-Ad₃PN)HfMe₂ Catalyst² Example(Inventive) Temp. (°C) Scavenger 1-C8/C2 (wt/wt) Al/Hf (mol/mol) BHEB/Hf(mol/mol) BHEB/Al (mol/mol) Activity k_(p) Ethylene Conversion % 1 190MAO 0.15 80 8 0.1 10158 89.8 2 190 MAO 0.5 80 8 0.1 9973 89.63 3 160 MAO0.5 80 8 0.1 21520 89.91 Note 2: The (Ph₃C)[B(C₆F₅)₄]/Hf ratio was 1.2;1-octene (“1-C8”)/ethylene (“C2”) ratio; BHEB =2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-Adamantyl; Cp* =pentamethylcyclopentadienyl.

TABLE 3 Polymerization Results with Cp*(1-Ad₃PN)Hf(CH₂Ph)₂ Catalyst³Example (Inventive) Temp (°C) Scavenger (Ph₃C)[B(C₆F₅)₄ /Hf (mol/mol)1-C8/C2 (wt/wt) Al/Hf (mol/mol) BHEB/Hf (mol/mol) 4 160 MAO 1.20 0.5 8024 5 160 MAO 1.20 0.5 80 0 6 160 MAO 1.20 0.5 4.98 0 7 190 MAO 1.20 0.55.01 0 8 160 TnOAI 1.12 0.5 4.73 0 9 160 Et₂AlOEt 1.12 0.5 3.54 0

TABLE 3 - CONTINUED Polymerization Results with Cp*(1-Ad₃PN)Hf(CH₂Ph)₂Catalyst³ Example (Inventive) BHEB/Al (mol/mol) Activity (k_(p))Ethylene Conversion (%) SCB/1000C Mw PD (Mw/Mn) 4 0.3 20,950 90.32 12.031,082 1.91 5 0.0 16,736 90.26 13.3 29,509 1.90 6 0.0 18,462 90.11 12.630,758 1.84 7 0.0 12,932 92.11 12.6 19,180 1.93 8 0.0 11,560 89.95 11.632,499 1.91 9 0.0 8,136 89.36 10.8 33,941 1.77 Note 3: 1-octene = 1-C8;ethylene = C2; BHEB = 2,6-di-tert-butyl-4-ethylphenol; TnOAI =tri(n-octyl)aluminum; 1-Ad = 1-Adamantyl; Cp* =pentamethylcyclopentadienyl.

Table 2 shows that at 160° C., the Cp*(1-Ad₃PN)HfMe₂ catalyst achievedextremely high activity with a k_(p) of 21520 (Inv. Example 3) with MAOas scavenger with 0.1 equivalent of BHEB. When polymerizationtemperature was increased to 190° C. (Inv. Examples 1 and 2), thecatalyst activity was still very high with a k_(p) of 10158 and 9973,respectively.

Table 3 shows the polymerization results with Cp*(1-Ad₃PN)Hf(CH₂Ph)₂catalyst which has different activatable ligands in comparison toCp*(1-Ad₃PN)HfMe₂. At 160° C., in the presence of scavenger (MAO/BHEB),the catalyst system achieved extremely high activity with a k_(p) of20950 (Inv. Example 4). At the same temperature (Inv. Example 5), whileusing only MAO as scavenger (i.e., without the use of bulky phenolBHEB), the catalyst system still achieved very high activity with ak_(p) of 16763. When the Al/Hf ratio was decreased from 80 to 4.98 (Inv.Example 6), very high activity was still achieved, with a k_(p) of18462. Even at 190° C. (Inv. Example 7), the catalyst activity was stillvery high with a k_(p) of 12932. Finally, when the polymerization wascarried out using simple aluminum alkyls as a scavenger, such as TnOAIand Et₂AlOEt, and in the absence of BHEB, the catalyst activity wasstill very high with k_(p)’s of greater than 8000 (Inv. Examples 8 and9).

Further polymerization results employing further catalyst complexderivatives having a cylcopentadientyl type ligand and a phosphinimineligand bearing an adamantyl moiety (including substituted adamantylmoieties and unsubstituted adamantyl moieties) are reported in Tables 4and 5. Further complexes based on hafnium and their polymerizationresults are provided in Table 4, while complexes based on zirconium andtheir polymerization results are provided in Table 5. The polymers weremade using a continuous solution polymerization process in a CPU unit asalready described above.

TABLE 4 Polymerization Results with Other Hafnium 1-AdamantylPhosphinimine Catalysts⁴ Example, Complex (Inventive) Temp. (°C)Activator Al/Hf (mol/mol) BHEB/Al (mol/mol) C8/C2 (wt/wt) 10,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 45 0.3 0.15 11,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 43 0.3 0.30 12,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 43 0.3 0.50 13,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 45 0 0.50 14,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 25 0.3 0 15,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 28 0.3 0.15 16,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 28 0.3 0.30 17,Cp*((1-Ad′)₂(1-Ad)PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 25 0.3 0.50 18,(3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 62 0.3 0.1519, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 62 0.30.30 20, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 540.3 0.50 21, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄]48 0 0.50 22, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 190 [Ph₃C][B(C₆F₅)₄]43 0.3 0 23, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 190 [Ph₃C][B(C₆F₅)₄]43 0.3 0.15 24, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 190[Ph₃C][B(C₆F₅)₄] 43 0.3 0.30 25, (3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂190 [Ph₃C][B(C₆F₅)₄] 54 0.3 0.50 26, [(C₆F₅CH₂)(CH₃)₄C₃]((1-Ad)₃P=N)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 48 0.3 0.00 27,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 48 0.3 0.1528, [(C₆F₅CH₂)(CH₃)₄Cp]((1 -Ad)₃P=N)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 43 0.30.30 29, [(C₆F₅CH₂)(CH₃)₄Cp]((1 -Ad)₃P=N)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 430.3 0.50 30, [(C₆F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄]54 0 0.50 31, [(C₆F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 140 B(C₆F₅)₃ 0.960.3 0.30 32, [(C₆F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄]19.29 0.3 0.00 33, [(C₆F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 190[Ph₃C][B(C₆F₅)₄] 20.77 0.3 0.15 34, [(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 22.50 0.3 0.30 35,[(C₆F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 20.77 0.30.50 36, n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 13.50 0.3 0.00 37,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 13.50 0.3 0.15 38,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 13.50 0.3 0.30 39,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 13.50 0.3 0.50 40,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 [Ph₃C][B(C₆F₅)₄] 14.59 0 0.50 41,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 140 B(C₆F₅)₃ 0.89 0.3 0.30 42,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 2 0.3 0.00 43,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 2 0.3 0.15 44,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 2 0.3 0.30 45,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 190 [Ph₃C][B(C₆F₅)₄] 2 0.3 0.50 46,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 48 0.30.00 47, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140[Ph₃C][B(C₆F₅)₄] 43.20 0.3 0.15 48,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 43.200.3 0.30 49, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140[Ph₃C][B(C₆F₅)₄] 36 0.3 0.50 50,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140 [Ph₃C][B(C₆F₅)₄] 36 00.50 51, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 140 B(C₆F₅)₃ 3.380.3 0.30 52, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 190[Ph₃C][B(C₆F₅)₄] 15.43 0.3 0.00 53,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 190 [Ph₃C][B(C₆F₅)₄] 15.430.3 0.15 54, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 190[Ph₃C][B(C₆F₅)₄] 15.43 0.3 0.30 55,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 190 [Ph₃C][B(C₆F₅)₄] 15.430.3 0.50 56, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 190[Ph₃C][B(C₆F₅)₄] 15.43 0 0.5 Note 4: Scavenger = MAO; Al concentrationin the reactor was 20 umol/L; [Ph₃C][B(C₆F₅)₄]/Hf molar ratio = 1.2;B(C₆F₅)₃/Hf molar ratio = 1.2; BHEB = 2,6-di-tert-butyl-4-ethylphenol;(Ph-Indolyl)(1,2,3-Me₃Cp =1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl; 1-Ad = 1-Adamantyl;1-Ad′ =3,5-Me₂-1-Ad, Cp* = pentamethylcyclopentadienyl.

TABLE 4 - CONTINUED Polymerization Results with Other Hafnium1-Adamantyl Phosphinimine Catalysts⁴ Example, Complex (Inventive)Ethylene Conversion (%) Activity (k_(p)) SCB/1000C Mw PD Mw/Mn 10,Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 90.14 7,995 11, Cp*((1-Ad′)₂(1-d)PN)HfBn₂90.44 7,859 12, Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 89.34 6,963 12.3 41,573 2.0213, Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 90.49 8,321 14, Cp*((1-Ad′)₂(1-d)PN)HfBn₂90.53 4,672 0.6 27,144 1.98 15, Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 89.31 4,5073.2 25,998 2.24 16, Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 89.67 4,683 6 24,731 2.0417, Cp*((1-Ad′)₂(1-d)PN)HfBn₂ 90.20 4,498 9.5 23,142 2.12 18,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 90.60 11,439 19,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 89.3 9,905 20,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 90.2 9,558 16.4 50,712 1.82 21,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 89.75 8,083 22,(3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 89.08 6,777 1.3 32,740 2.07 23,(3,5-tBu₂-Ph-Me₄Cp)((1- Ad)₃PN)HfMe₂ 89.63 7,181 4.2 28,528 1.89 24,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 90.03 7,502 7.9 26,289 1.9 25,(3,5-tBu₂-Ph-Me₄Cp)((1-Ad)₃PN)HfMe₂ 90.92 10,398 11.6 22,719 1.9 26,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 89.79 8,118 <0.5 49,053 1.84 27,[(C₃F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 89.02 7,484 4.2 44,126 1.72 28,[(C₃F₅CH₂)(CH₃)₄Cp]((1- Ad)₃P=N)HfBn₂ 90.7 8,102 8.9 37,739 1.89 29,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 90.37 7,796 13.7 34,292 1.93 30,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 89.21 8,586 13.2 35,813 1.89 31,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 89.4 156 5.9 36,873 2.12 32,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 90.27 3,441 1.8 12,510 2.43 33,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 90.31 3,722 4.9 13,376 2.17 34,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 89.63 3,740 7.1 13,604 2.03 35,[(C₆F₅CH₂)(CH₃)₄Cp]((1-Ad)₃P=N)HfBn₂ 90.55 3,827 12.1 11,781 3.43 36,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.40 2,190 <0.5 58,756 1.74 37,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.76 2,276 4.7 53,406 1.77 38,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 90.45 2,459 9.7 50,981 2.37 39,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 90.94 2,606 15.1 48,566 1.7 40,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 90.38 2,637 15.6 49,385 1.85 41,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.33 143 8.2 66,457 1.72 42,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.28 333 0.8 29,275 2.00 43,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.4 337 4.1 27,045 1.89 44,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.48 340 6.5 24,177 2.39 45,n-Pr₅Cp((1-Ad)₃PN)HfBn₂ 89.53 342 10.4 24,495 1.97 46,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.08 8,382 1.5 35,141 2.0347, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.15 7,603 8.5 29,8022.16 48, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 89.41 7,014 13.226,483 2.07 49, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.25 6,40820.4 23,516 2.17 50, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.326,460 21.6 20,524 2.47 51, [(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂90.1 591 13.3 31,165 2.02 52,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.75 2,911 53,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.50 2,826 54,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.48 2,820 55,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 90.50 2,826 56,[(Ph-Indolyl)(1,2,3-Me₃Cp)]((1-Ad)₃P=N)HfMe₂ 89.73 2,592 Note 4:Scavenger = MAO; Al concentration in the reactor was 20 umol/L;[Ph₃C][B(C₆F₅)₄]/Hf molar ratio = 1.2; B(C₆F₅)₃/Hf molar ratio = 1.2;BHEB = 2,6-di-tert-butyl-4-ethylphenol; (Ph-Indolyl)(1,2,3-Me₃Cp =1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl; 1-Ad = 1-Adamantyl;1-Ad′ =3,5-Me₂-1-Ad, Cp* = pentamethylcyclopentadienyl.

TABLE 5 Polymerization Results with Zirconium 1-Adamantyl PhosphinimineCatalysts⁵ Example, Complex (Inventive) Temp. (°C) Activator Al/Zr(mol/mol) BHEB/Al (mol/mol) C8/C2 (wt/wt) 57, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 66 0.3 0.15 58, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 64 0.3 0.30 59, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 64 0.3 0.50 60, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 140 B(C₆F₅)₃ 13.5 0.3 0.30 61, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 36 0.3 0 62, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 36 0.3 0.15 63, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 36 0.3 0.30 64, Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 54 0.3 0.50 65,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 98 0.3 0.15 66,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 83 0.3 0.30 67,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 140 [Ph₃C][B(C₆F₅)₄] 65 0.3 0.50 68,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 140 B(C₆F₅)₃ 48 0.3 0.30 69,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 47 0.3 0 70,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 51 0.3 0.15 71,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 49 0.3 0.30 72,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 68 0.3 0.50 73,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 190 [Ph₃C][B(C₆F₅)₄] 47 0.3 0.50 74,Cp((1-Ad)₃PN)ZrMe₂ 140 [Ph₃C][B(C₆F₅)₄] 54.00 0.3 0.00 75,Cp((1-Ad)₃PN)ZrMe₂ 140 [Ph₃C][B(C₆F₅)₄] 33.23 0.3 0.15 76,Cp((1-Ad)₃PN)ZrMe₂ 140 [Ph₃C][B(C₆F₅)₄] 12.71 0.3 0.30 77,Cp((1-Ad)₃PN)ZrMe₂ 140 [Ph₃C][B(C₆F₅)₄] 5.40 0.3 0.50 78,Cp((1-Ad)₃PN)ZrMe₂ 190 [Ph₃C][B(C₆F₅)₄] 3.38 0.3 0.00 79,Cp((1-Ad)₃PN)ZrMe₂ 190 [Ph₃C][B(C₆F₅)₄] 2.88 0.3 0.15 80,Cp((1-Ad)₃PN)ZrMe₂ 190 [Ph₃C][B(C₆F₅)₄] 2.70 0.3 0.30 81,Cp((1-Ad)₃PN)ZrMe₂ 190 [Ph₃C][B(C₆F₅)₄] 2.40 0.3 0.50 Note 5: Scavenger= MAO; Al concentration in the reactor was 20 umol/L;[Ph₃C][B(C₆F₅)₄]/Zr molar ratio = 1.2; B(C₆F₅)₃/Zr molar ratio = 1.2;BHEB = 2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-Adamantyl; 1-Ad′=3,5-Me₂-1-Ad, Cp* = pentamethylcyclopentadienyl; Cp = cyclopentadienyl.

TABLE 5 - CONTINUED Polymerization Results with Zirconium 1-AdamantylPhosphinimine Catalysts⁵ Example, Complex (Inventive) EthyleneConversion (%) Activity (k_(p)) SCB/1000C Mw PD Mw/Mn 57,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.43 12,077 1.4 33,461 2.2 58,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.65 11,933 3.4 28,982 2.04 59,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.01 11,089 5.5 25,420 1.9 60,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.27 2,409 3.1 25,432 1.86 61,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.27 6,423 <0.5 18,055 1.94 62,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 89.50 5,901 1.3 17,576 1.88 63,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.18 6,358 2.7 16,826 1.76 64,Cp*((1-Ad′)₂(1-Ad)PN)Zr(CH₂Ph)₂ 90.53 9,927 4.4 14,732 2.01 65,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 89.50 16,094 66, Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.314,873 67, Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 91.38 13,344 n/a n/a n/a 68,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.36 8,652 3.2 29,233 1.98 69,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.78 8,891 <0.5 18,297 2.02 70,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.29 9,196 1.3 17,572 1.7 71,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.73 9,240 3.6 16,915 1.89 72,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 89.31 10,854 4.5 16,483 1.9 73,Cp*((1-Ad)₃PN)Zr(CH₂Ph)₂ 90.12 8,237 4.3 16,832 1.89 74,Cp((1-Ad)₃PN)ZrMe₂ 90.38 9,756 75, Cp((1-Ad)₃PN)ZrMe₂ 89.38 5,378 76,Cp((1-Ad)₃PN)ZrMe₂ 89.00 1,977 77, Cp((1-Ad)₃PN)ZrMe₂ 89.00 840 78,Cp((1-Ad)₃PN)ZrMe₂ 89.31 542 2.8 15,302 4.11 79, Cp((1-Ad)₃PN)ZrMe₂89.61 478 6.7 10,291 3.5 80, Cp((1-Ad)₃PN)ZrMe₂ 89.51 443 9.5 7,354 2.981, Cp((1-Ad)₃PN)ZrMe₂ 89.90 411 15.3 5,524 3.2 Note 5: Scavenger = MAO;Al concentration in the reactor was 20 umol/L; [Ph₃C][B(C₆F₅)₄]/Zr molarratio = 1.2; B(C₆F₅)₃/Zr molar ratio = 1.2; BHEB =2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-Adamantyl; 1-Ad′=3,5-Me₂-1-Ad, Cp* = pentamethylcyclopentadienyl; Cp = cyclopentadienyl.

The data provided in Tables 4 and 5, show that further hafnium based andzirconium based complexes having a cyclopentadienyl type ligand and aphosphinimine ligand bearing an unsubstituted or substituted adamantylmoiety may be employed in active olefin polymerization catalyst systems,in olefin polymerization processes such as a solution phase olefinpolymerization process.

Non-limiting embodiments of the present disclosure include thefollowing: Embodiment A. A complex having the formula (PI)(Cp)ML₂,wherein:

-   I) PI is a phosphinimine ligand defined by the formula:

-   

-   where N is a nitrogen atom; P is a phosphorus atom; each R¹ is    unsubstituted adamantyl, or substituted adamantyl; and R^(1′) is    selected from the group consisting of unsubstituted adamantyl,    substituted adamantyl and C₁ to C₆ hydrocarbyl;

-   II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered    carbon ring having delocalized bonding within the ring and bound to    M, which rings are unsubstituted or may be further substituted;

-   III) each L is an activatable ligand; and

-   IV) M is zirconium or hafnium.

Embodiment B. The complex according to Embodiment A wherein R¹ isunsubstituted adamantyl, or substituted adamantyl.

Embodiment C. The complex according to Embodiment A wherein R¹ isunsubstituted adamantyl.

Embodiment D. The complex according to Embodiment A, B or C wherein eachR¹ is unsubstituted adamantyl.

Embodiment E. The complex according to Embodiment A wherein R^(1′) andeach R¹ is 1-adamantyl.

Embodiment F. The complex according to Embodiment A, B, C, D or Ewherein Cp is (pentamethyl)cyclopentadienyl.

Embodiment G. The complex according to Embodiment A, B, C, D or Ewherein Cp is cyclopentadienyl.

Embodiment H. The complex according to Embodiment A, B, C, D, E, F or Gwherein M is zirconium.

Embodiment 1. The complex according to Embodiment A, B, C, D, E, F or Gwherein M is hafnium.

Embodiment J. An olefin polymerization catalyst system comprising:

-   A) a complex having the formula (Pl)(Cp)ML₂, wherein:    -   I) Pl is a phosphinimine ligand defined by the formula:

    -   

    -   where N is a nitrogen atom; P is a phosphorus atom; each R¹ is        unsubstituted adamantyl, or substituted adamantyl; and R^(1′) is        selected from the group consisting of unsubstituted adamantyl,        substituted adamantyl and C₁ to C₆ hydrocarbyl;

    -   II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered        carbon ring having delocalized bonding within the ring and bound        to M, which rings are unsubstituted or may be further        substituted;

    -   III) each L is an activatable ligand; and

    -   IV) M is zirconium or hafnium; and-   B) an activator.

Embodiment K. The olefin polymerization catalyst system according toEmbodiment I wherein the activator is selected from the group consistingof an aluminoxane; an organoaluminum compound; an ionic activator; andmixtures thereof.

Embodiment L. The olefin polymerization catalyst system according toEmbodiment J or K wherein R^(1′) is unsubstituted adamantyl, orsubstituted adamantyl.

Embodiment M. The olefin polymerization catalyst system according toEmbodiment J or K wherein R^(1′) is unsubstituted adamantyl.

Embodiment N. The olefin polymerization catalyst system according toclaim Embodiment J, K, L or M wherein each R¹ is unsubstitutedadamantyl.

Embodiment O. The olefin polymerization catalyst system according toclaim Embodiment J or K wherein R^(1′) and each R¹ is 1-adamantyl.

Embodiment P. The olefin polymerization catalyst system accordingEmbodiment J, K, L, M, N or O wherein Cp is (pentamethyl)cyclopentadienyl.

Embodiment Q. The olefin polymerization catalyst system according toEmbodiment J, K, L, M, N or O wherein Cp is cyclopentadienyl.

Embodiment R. The olefin polymerization catalyst system according toEmbodiment J, K, L, M, N, O, P or Q wherein M is zirconium.

Embodiment S. The olefin polymerization catalyst system according toEmbodiment J, K, L, M, N, O, P or Q wherein M is hafnium.

Embodiment T. A process for the polymerization of olefins comprisingcontacting one or more of ethylene and C₃ to C₁₀ alpha olefins with theolefin polymerization catalyst system according to any one of claimsEmbodiment J, K, L, M, N, O, P, Q, R or S under polymerizationconditions.

Embodiment U. The process according to Embodiment T wherein the one ormore of ethylene and C₃ to C₁₀ alpha olefins consists of a) ethylene;and b) one or more olefins selected from the group consisting of1-butene; 1-hexene; and 1-octene.

Embodiment V. A process for the (co) polymerization of ethylenecomprising:

-   A) preparing a first polymer solution by polymerizing ethylene,    optionally with one or more C₃ to C₁₀ alpha olefins, in a solvent in    a first polymerization reactor at a temperature of from 80 to    200° C. and a pressure of from 1,000 to 8,000 psi in the presence    of (i) the complex according to Embodiment A; and (ii) an activator    consisting essentially of an aluminoxane and an ionic activator; and-   B) passing said first polymer solution into a second polymerization    reactor and (co) polymerizing ethylene, optionally with one or more    C₃-C₁₀ alpha olefins, in the presence of a Ziegler Natta catalyst.

Embodiment W. A process for the (co) polymerization of ethylenecomprising:

-   A) preparing a first polymer solution by polymerizing ethylene,    optionally with one or more C₃ to C₁₀ alpha olefins, in a solvent in    a first polymerization reactor at a temperature of from 80 to    200° C. and a pressure of from 1,000 to 8,000 psi in the presence    of (i) the complex according to Embodiment A; and (ii) an activator    consisting essentially of an organoaluminum compound and an ionic    activator; and-   B) passing said first polymer solution into a second polymerization    reactor and (co) polymerizing ethylene, optionally with one or more    C₃-C₁₀ alpha olefins, in the presence of a Ziegler Natta catalyst.

INDUSTRIAL APPLICABILITY

Provided are zirconium and hafnium complexes which have acyclopentadienyl type ligand and a phosphinimine ligand bearing anadamantyl (unsubstituted or substituted) moiety. The new complexes areactive in the polymerization of ethylene with an alpha olefin.

1. A complex having the formula (PI)(Cp)ML₂, wherein: I) PI is aphosphinimine ligand defined by the formula:

where N is a nitrogen atom; P is a phosphorus atom; each R¹ isunsubstituted adamantyl, or substituted adamantyl; and R^(1′) isselected from the group consisting of unsubstituted adamantyl,substituted adamantyl and C₁ to C₆ hydrocarbyl; II) Cp is acyclopentadienyl-type ligand comprising a 5-membered carbon ring havingdelocalized bonding within the ring and bound to M, which ring isunsubstituted or may be further substituted; III) each L is anactivatable ligand; and IV) M is zirconium or hafnium.
 2. The complex ofclaim 1, wherein R^(1′) is unsubstituted adamantyl, or substitutedadamantyl.
 3. The complex of claim 1, wherein R^(1′) is unsubstitutedadamantyl.
 4. The complex of claim 3, wherein each R¹ is unsubstitutedadamantyl.
 5. The complex of claim 4, wherein R^(1′) and each R¹ is1-adamantyl.
 6. The complex of claim 1, wherein Cp is (pentamethyl)cyclopentadienyl.
 7. The complex of claim 1, wherein Cp iscyclopentadienyl.
 8. The complex of claim 1, wherein M is zirconium. 9.The complex of claim 1, wherein M is hafnium.
 10. An olefinpolymerization catalyst system comprising: A) a complex having theformula (PI)(Cp)ML₂, wherein: I) PI is a phosphinimine ligand defined bythe formula:

where N is a nitrogen atom; P is a phosphorus atom; each R¹ isunsubstituted adamantyl, or substituted adamantyl; and R^(1′) isselected from the group consisting of unsubstituted adamantyl,substituted adamantyl and C₁ to C₆ hydrocarbyl; II) Cp is acyclopentadienyl-type ligand comprising a 5-membered carbon ring havingdelocalized bonding within the ring and bound to M, which ring isunsubstituted or may be further substituted; III) each L is anactivatable ligand; and IV) M is zirconium or hafnium; and B) anactivator.
 11. The olefin polymerization catalyst of claim 10, whereinthe activator is selected from the group consisting of an aluminoxane;an organoaluminum compound; an ionic activator; and mixtures thereof.12. The olefin polymerization catalyst of claim 10, wherein R^(1′) isunsubstituted adamantyl, or substituted adamantyl.
 13. The olefinpolymerization catalyst of claim 10, wherein R^(1′) is unsubstitutedadamantyl.
 14. The olefin polymerization catalyst of claim 13, whereineach R¹ is unsubstituted adamantyl.
 15. The olefin polymerizationcatalyst of claim 14, wherein R^(1′) and each R¹ is 1-adamantyl.
 16. Theolefin polymerization catalyst system of claim 10, wherein Cp is(pentamethyl)cyclopentadienyl.
 17. The olefin polymerization catalystsystem of claim 10, wherein Cp is cyclopentadienyl.
 18. The olefinpolymerization catalyst system of claim 10, wherein M is zirconium. 19.The olefin polymerization catalyst system of claim 10, wherein M ishafnium.
 20. A process for the polymerization of olefins, the processcomprising contacting one or more of ethylene and C₃ to C₁₀ alphaolefins with the olefin polymerization catalyst system of claim 10 underpolymerization conditions.
 21. The process according to claim 20 whereinthe one or more of ethylene and C₃ to C₁₀ alpha olefins consists of a)ethylene; and b) one or more olefins selected from the group consistingof 1-butene; 1-hexene; and 1-octene.
 22. A process for the (co)polymerization of ethylene, the process comprising: A) preparing a firstpolymer solution by polymerizing ethylene, optionally with one or moreC₃ to C₁₀ alpha olefins, in a solvent in a first polymerization reactorat a temperature of from 80 to 200° C. and a pressure of from 1,000 to8,000 psi in the presence of (i) the complex according to claim 1; and(ii) an activator consisting essentially of an aluminoxane and an ionicactivator; and B) passing said first polymer solution into a secondpolymerization reactor and (co) polymerizing ethylene, optionally withone or more C₃-C₁₀ alpha olefins, in the presence of a Ziegler Nattacatalyst.
 23. A process for the (co) polymerization of ethylene, theprocess comprising: A) preparing a first polymer solution bypolymerizing ethylene, optionally with one or more C₃ to C₁₀ alphaolefins, in a solvent in a first polymerization reactor at a temperatureof from 80 to 200° C. and a pressure of from 1,000 to 8,000 psi in thepresence of (i) the complex according to claim 1; and (ii) an activatorconsisting essentially of an organoaluminum compound and an ionicactivator; and B) passing said first polymer solution into a secondpolymerization reactor and (co) polymerizing ethylene, optionally withone or more C₃-C₁₀ alpha olefins, in the presence of a Ziegler Nattacatalyst.